JPS60208055A - Manufacture of nonaqueous solvent battery - Google Patents

Abstract

PURPOSE:To obtain a battery whose voltage drop in an initial stage of high rate discharge is small and recovery time of voltage is short by performing a specified capacity of discharge as post-treatment after assembly of a nonaqueous solvent battery. CONSTITUTION:A negative electrode 2 such as lithium and a positive electrode 3 are accommodated into a can 1 with separators 41 and 42 interposed between them, then electrolyte 13 which also serves as positive active material mainly comprising sulfur oxyhalide is put therein to fabricate a nonaqueous solvent battery. After the battery was assembled, preferably within 10 days, the battery is discharged by 0.5-10% of the total discharge capacity by constant current discharge procedure. By this post-treatment, a battery having good discharge performance whose voltage or current is steady is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for manufacturing a non-aqueous solvent battery, and more particularly to a method for manufacturing a non-aqueous battery with improved post-processing after battery assembly.

[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, so they are used in calculators, watches, and memory devices. It is often used as a backup battery. Among them, lithium is used for the negative electrode, and thionyl chloride (SOCl2) is used as the positive electrode active material.
Batteries using sulfur oxynodecadides, such as sulfuryl chloride (SO2Cl2), are attracting attention because of their particularly high energy density. These batteries have a positive electrode made of carbon and a metal current collector, and are generally made of sulfur, which is a mixture of a Lewis acid such as aluminum chloride (HTCT3) or aluminum bromide (AtBr3) and a Lewis base such as lithium chloride or lithium bromide. Liquid oxyno-rhodanide is used as the electrolyte. Therefore, a liquid oxyhalide can be used 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 LiCt film which is a reaction product is generated on the surface of the negative electrode lithium. This LICtIC has a function of preventing direct contact between the negative electrode lithium and the oxyhalide, 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 in the case of wood/current discharge, and especially when stored at high temperatures for long periods of time, the growth of the LICl film can occur considerably. After discharge or during discharge at low temperatures, a significant voltage drop occurs at the beginning of discharge.
There was a problem in that it required a considerable amount of time to recover to a predetermined voltage.

[Purpose of the invention]

The present invention has a small voltage drop even at the initial stage of large current discharge,
The present invention also aims to provide a method for manufacturing a non-aqueous solvent battery that has a short voltage recovery time.

[Summary of the Invention] The present invention stores a negative electrode and a positive electrode made of a light metal such as lithium in a battery container with a separator interposed therebetween, and the container also serves as a positive electrode active material mainly composed of sulfur oxyhalide. In manufacturing a nonaqueous solvent battery having a structure containing an electrolyte, after assembling the battery, O1 of the total discharge capacity of the battery is
This method is characterized by performing 5 to 10 discharges as a post-treatment. According to the method of the present invention, it is possible to obtain a non-aqueous solvent battery that does not show a significant voltage drop even when subjected to large current discharge after storage and has a short voltage recovery time. The reason why such excellent characteristics can be exhibited is considered to be that the discharge reaction product exhibits an inhibitory effect on the growth of the LiCt film on the lithium negative electrode.

Moreover, by performing the above-mentioned post-processing, it can be expected that a battery having stable characteristics with constant voltage and current values can be supplied.

The reason for limiting the discharge capacity during the above post-treatment is that if the discharge capacity is less than 0.5% of the total discharge capacity of the battery, the post-treatment will not be able to sufficiently suppress the voltage drop. This is because if the discharge capacity exceeds 10 inches, the above-mentioned effect will not increase and the battery life will be negative. It is desirable that such post-treatment be performed within 10 days after the battery is assembled. The reason for this is that even if post-treatment is performed after a long period of time exceeding 10 days, the voltage drop suppressing effect may not be sufficiently exerted.

[Embodiments of the invention]

Next, embodiments of the present invention will be described in detail with reference to the drawings.

Examples 1 to 4 First, a cylindrical negative electrode 2 made of metallic lithium was crimped into a bottomed cylindrical stainless steel can body 1 with an open upper surface that also served as a negative electrode terminal. Next, the negative electrode 2 of the can body)
A positive electrode 3 is disposed inside the negative electrode 2 and a nanolayer plate made of a nonwoven glass fiber fabric is placed on the inner surface of the negative electrode 2 and the bottom surface of the can body 1.
+4. This positive electrode 3 consists of a cylindrical porous carbon body 5 made of carzen black using polytetrafluoroethylene as a binder, and a metal collection consisting of a cylindrical wire mesh placed inside the hollow part of the porous carbon body 5. It is composed of an electric body 6.

Such a positive electrode 3 can be prepared, for example, by blending a commercially available polytetrafluoroethylene emulsion into a Boolean black at a ratio of 10 wt%, adding water and ethyl alcohol, and then adding water and ethyl alcohol to the mixture at room temperature.
After stirring for a period of time, kneading is carried out. 2. A metal current collector 6 made of KEL wire mesh is crimped to form a cylindrical body with the current collector 6 facing inside, and then dried under vacuum at 150°C. It is produced by using the porous carbon body 5 as the crosstalk sheet.

Next, an insulating paper 7 having a hole in the center was housed and supported above the separator 4□ in the can body 1. Next, a lid body 11 made of stainless steel, which has a hole 8 in the center and into which a positive terminal 10 made of a stainless steel pipe for liquid injection is inserted through a metal-glass sealing material 9, is prepared. Common form 1
After connecting the lead wire 12 to the lower end of the positive electrode terminal 10 of the can body 1 and connecting the other end of the lead wire 12 to the metal current collector 6 inside the can body 1, the lid body II is inserted into the upper opening of the can body. mated to. Subsequently, the upper end opening in the can body J and the fitted lid 11 were welded using a Rede welding tube to seal the lid 1 in a liquid-tight manner.

Next, an electrolytic solution was injected from the pipe-shaped positive electrode terminal 10 of the lid 1, and the electrolytic solution J3 was accommodated in the can body 1. The electrolytic solution used was one in which 1.5 moyb/aluminum chloride (htct5) and lithium chloride (LICt) were each dissolved in thionyl chloride (5ocz2). Next, a stainless steel envelope 14 was inserted into the tube-shaped positive terminal 10, and the tip of the positive terminal 10 and the envelope 14 were laser welded to seal the hole of the terminal JO to assemble the battery. .

Next, four batteries obtained within 10 days after assembly were set in a constant current discharge device, and each battery was discharged at a constant current of 50 mA to 0.5% of the total discharge capacity.

Four types of batteries were manufactured by performing discharges of 2.5%, 5chi, and 10chi.

Comparative Example A battery having the same structure as that of the example was manufactured except that no post-treatment by discharging was performed after battery assembly.

Therefore, regarding the batteries of Examples 1 to 4 and Comparative Example,
After being stored at 25°C for 3 months after manufacture, a constant resistance discharge of 30Ω was performed, and after the discharge started, the voltage was 3. When the time taken to recover to Ov was measured, the results shown in the table below were obtained. In addition, in the same table, as Reference Examples 1 and 2, after battery assembly, by discharging 0.2fi and 12% of the total discharge capacity of the battery using the same constant current discharge device as in the example, The manufactured batteries are also listed.

As is clear from the table above, the batteries of Examples 1 to 4 and Reference Examples 1 and 2, which were subjected to post-treatment by discharging after battery assembly, had a shorter voltage recovery time than the batteries that were not subjected to post-treatment (comparative example). It can be seen that it becomes shorter. Further, when the discharge capacity is set to 05 to 10% as in the present embodiment, the rotation time is within 5 seconds, which is significantly superior to that of the reference example IK. In addition, a battery with a discharge capacity of 12 inches (Reference Example 2) f'i discharge capacity of 10
The voltage recovery time is the same as that of the battery of Example 4, which was
It can be seen that the voltage recovery time does not change even after discharging more than 10%, indicating that the battery of Reference Example 2 is disadvantageous in terms of service life.

In addition, the voltage drop at the start of discharge is as follows:
9V, whereas in Example 2 (discharge rate 2.
It was found that the voltage drop of the 5%) O battery only dropped to 2.55V, and the voltage drop was small.

〔Effect of the invention〕

As detailed above, according to the present invention, it is possible to provide a method for manufacturing a non-aqueous solvent battery that has excellent initial discharge characteristics, such as suppressing voltage drop and shortening voltage recovery time even at the initial stage of large current discharge.

[Brief explanation of drawings]

The figure is a sectional view of a non-aqueous solvent battery assembled in an embodiment of the present invention. l... Can body, 2... Negative electrode, 3... Positive electrode, 'I+1
! ... Separator, 5... Porous carbon body, 6...
・Metal current collector, 10...pipe-shaped positive electrode terminal, 1 no.
... Lid, J3... Electrolyte. Applicant's representative Patent attorney Takehiko Suzue Continued from page 1 0 Inventor Yu Sahara - [Partner] Inventor Yoshiyasu Aoki @ Inventor Kazuya Hiratsuka

Claims (1)

[Claims] A negative electrode and a positive electrode made of a light metal are housed in a battery container with a separator interposed therebetween, and an electrode which also serves as a positive electrode active material whose main component is sulfur oxyhalodanide is placed in the container! ! IQ
A method for manufacturing a non-aqueous solvent battery, characterized in that after the battery is assembled, a discharge of 0.5 to 10% of the total discharge capacity of the battery is performed as a post-treatment. .