JPH0215560A - Manufacture of nonaqueous solvent battery - Google Patents

Abstract

PURPOSE:To make it possible to manufacture a nonaqueous solvent battery being of structure formed through a process of liquid-tightly sealing the opening of an electrolyte filler pipe made of metal serving also as the other polar terminal, by abutting the flange portion at the top of a plug body onto the upper end plane of a pipe, caulking the part of the pipe protruded from a covering body to stick the inner circumferential plane of the pipe fast to the outer circumferential plane of the plug body and subsequently welding the flange portion to the pipe for sealingly closing the opening. CONSTITUTION:A metallic covering body 8 having a metallic pipe 10 also serving as the other polar terminal liquid-tightly fixed beforehand in a hole near the center of the covering body via an insulating material such that one end side of the pipe 10 may be protruded, is engaged with the upper opening of a metallic canister body 1, the opening is welded to be closed and electrolyte 13 is stored through the metallic pipe 10 into the canister body 1. Thereafter, a flange portion 14 is abutted onto the upper end plane of the pipe 10, the part of the pipe 10 protruded from the covering body 8 is then caulked to form an annular constricted portion 16 directed to an inside plug body 15 so as to stick the inner circumferential plane of the pipe 10 fast to the outer circumferential plane of the plug body 15, and the upper end plane of the pipe 10 is further welded to the flange portion 14 of the plug body 15 abutting on the upper end plane. This makes it possible to manufacture a nonaqueous solvent battery being of an excellently sealed structure which is formed to avoid any poor seal in sealingly closing the opening of the metallic pipe in order to prevent the electrolyte in use from its leaking.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for manufacturing a non-aqueous solvent battery.

[Conventional technology] Nonaqueous solvent batteries using lithium, sodium, etc. as negative electrode active materials have high energy density, excellent storage characteristics,
It also has a wide operating temperature range, and is often used as a backup power source for calculators, clocks, and memory. Among these batteries, batteries that use lithium as the negative electrode, sulfur or phosphorus oxyhalide such as thionyl chloride or sulfuryl chloride as the main positive electrode active material, and a positive electrode consisting of carbon and metal current collectors are particularly energy efficient. Because of the large density, l! , l:l has been done.

By the way, since the above-mentioned battery uses a highly corrosive sulfur or phosphorous oxyhalide such as thionyl chloride or sulfuryl chloride as the main positive electrode active material, the oxyhalide may leak out of the battery container and cause damage to the battery. It is necessary to seal the battery container liquid-tight to prevent corrosion of the stored equipment.

Further, the oxyhalide is in a liquid state and the electrolyte is 114
Because the electrolyte used in the container is highly volatile and highly toxic, it is necessary to install power generation elements (negative electrode, separator , positive electrode), it is necessary to inject and store the electrolytic solution containing the oxyhalide in the same container.

For this reason, conventionally, when assembling the above-mentioned battery, the power generation element consisting of a negative electrode, a separator, and a positive electrode is first housed in a metal case that also serves as a negative polarity terminal, and the other polarity terminal is connected in advance with a glass or ceramic sealant. A metal pipe to which a metal pipe for liquid, which also serves as a liquid, is liquid-tightly fixed is fitted into the upper opening of the metal can body and sealed by laser welding, and then an electrolytic solution containing an oxyhalide is passed through the metal pipe. A method of injecting and storing the metal into the can body, further inserting a metal stopper into the metal pipe, and tightly sealing the end of the pipe protruding from the lid and the stopper at 71 by laser welding. has been considered.

[Problems to be Solved by the Invention] However, in this method, when welding the end of the metal pipe and the metal stopper, the electrolyte attached to the inner surface of the pipe or the metal near the lower end of the pipe; 1j the electrolyte in the body; This evaporates due to the heat during welding and enters the gaps in the form of gas, causing welding defects (in the case of pinholes), resulting in a decrease in yield.

The present invention has been made in order to solve the above-mentioned conventional problems, and includes a metal pipe for liquid injection that also serves as a terminal of the other polarity, which is liquid-tightly fixed to a metal lid through an insulating seal. We present a method for manufacturing a non-aqueous solvent battery with a sealed structure (j
L, L is what I'm trying to do.

[Means for Solving the Problems] The present invention includes a step of housing a negative electrode made of a light metal and a positive electrode mainly composed of porous carbon in a metal case that also serves as a -polar terminal, with a separator interposed therebetween; A metal lid body, in which a metal pipe that also serves as a terminal of the other polarity is liquid-tightly fixed to the hole through an insulating material so that one end side of the pipe protrudes in advance, is fitted into the upper opening of the metal body. and sealing by welding, and introducing an oxyhalide into the metal can through the metal pipe as a positive electrode? A step of accommodating an electrolytic solution contained as an L substance, and a step of inserting a metal plug into the metal pipe and sealing the end of the metal pipe protruding from the lid with the plug by welding. In manufacturing a non-aqueous solvent battery, a plug having a white flange on the upper end is used, and the plug is inserted into the metal pipe and the flange is applied to the upper end surface of the pipe. At the same time, the pipe portion protruding from the metal lid body is caulked to form an annular constriction toward the internal plug body, and the inner peripheral surface of the pipe and the outer peripheral surface of the plug body are brought into close contact with each other. ,
This method of manufacturing a non-aqueous solvent battery is characterized in that the upper end surface of the pipe and the flange of the stopper that abuts the upper end surface of the pipe are sealed by welding.

[Function] According to the present invention, a metal lid body is fixed in advance to a hole near the center in a liquid-tight manner through an insulating material so that a metal pipe that also serves as a terminal of the other polarity projects from one end side of the pipe. , after fitting into the upper opening of the metal can and sealing it by welding and storing the electrolyte in the metal can through the metal pipe, the flange is brought into contact with the upper end surface of the pipe, and the metal The pipe portion protruding from the lid is caulked to form an annular constriction toward the inner plug, thereby bringing the inner peripheral surface of the pipe and the outer peripheral surface of the plug closer together, and further tightening the upper end surface of the pipe. By welding the flange of the stopper and the flange of the stopper that come into contact with the flange, a non-aqueous solvent battery is manufactured that avoids sealing failure of the metal pipe and has a good sealing structure that prevents leakage of electrolyte during use. can.

[Example] Hereinafter, an example of the present invention will be described in detail with reference to FIGS. 1 and 2.

First, after crimping a cylindrical negative electrode 2 made of metallic lithium to the inner peripheral surface of a stainless steel can body 1 that also serves as a negative electrode terminal, a positive electrode 3 is placed inside the negative electrode 2 and inside the can body 1. The cathode 3 was housed through separators 4a and 4b made of, for example, glass U&91 nonwoven (1i) placed over the bottom surface of the can body 1. 10% by weight, water and ethyl alcohol were added, and the
After stirring for about an hour, the sheet is kneaded and pressed onto a metal current collector 5 made of a stainless steel net, and the sheet is dried in a vacuum at 150°C to form a porous carbon body 6 into a sheet shape. It was made by winding the body into a spiral shape.

Next, the separator 4 is placed in the can 1 above the positive electrode 3.
An insulating paper 7 having a hole in the center was placed supported by a.

Next, a stainless steel lid is fitted with a stainless steel pipe 10 for liquid injection, which also serves as a positive terminal, liquid-tightly fixed to the hole 9 opened in the center via a glass seal holder 11 so that its upper and lower ends protrude. After preparing a body 8 and connecting the lower end of the pipe 10 fixed to the lid body 8 to the metal current collector 5 of the positive electrode 3 via a lead wire 12, the pipe 10 is fitted into the upper opening of the can body l. and sealed by laser welding.

Next, a thionyl chloride solution (electrolytic solution) 13 in which, for example, 1.5 mol/Ω of LiAΩCg4 was dissolved was injected into the can body l through the pipe 10 and housed therein. Next, as shown in FIG. 2, a stainless steel plug 15 having a flange 14 having the same diameter as the outer diameter of the pipe IO is prepared at the upper end, and the plug 15 is placed inside the stainless steel vibe IO. The pipe was inserted until the flange 14 came into contact with the upper end surface of the pipe IO. Continuing, the pipe 1 protruding from the lid 8
After caulking the 0 portion to form an annular constriction 16 toward the plug 15 inside the pipe 10 and bring the inner peripheral surface of the pipe IO into close contact with the outer peripheral surface of the plug 15, the pipe 10
The non-aqueous solvent battery shown in FIG. 1 was manufactured by sealing the upper end surface of the battery and the flange portion 14 of the plug body 15 that was in contact therewith by laser welding.

According to the method described above, before the stainless steel pipe IO for liquid injection, which also serves as a positive electrode terminal, and the stainless steel stopper 15 are sealed by welding, the pipe IO is caulked to form an annular constriction toward the inner stopper 15. In order to form the portion 1G and bring the inner circumferential surface of the pipe 10 and the outer circumferential surface of the plug body 15 closer together,
When sealing is performed by welding, the electrolytic solution 13 in the can body l is gasified or liquefied due to the temperature rise during welding, and then the vibrator l
Movement to the upper end of the pipe IO can be prevented by the close contact between the pipe IO of the constricted portion 16 and the plug body 15. Moreover, even if the electrolytic solution should enter the upper side through the close contact part, a flange part 14 is formed at the upper end of the plug body 15, and it is brought into contact with the upper end surface of the pipe IO to seal it. Therefore, the electrolyte can be stopped before the relevant contact point. As a result, the electrolytic solution is stopped at two places, the contact area by the constriction part 16 and the lower surface of the flange part 14, and electrolysis between the upper end surface of the pipe IO to be welded and the flange part 14 of the plug body 15. Since adhesion of liquid can be prevented, it is possible to obtain a non-aqueous solvent battery with good sealing without the occurrence of pinholes by laser welding.

In fact, a battery manufactured according to this example and a stainless steel plug without a flange were inserted into a stainless steel pipe, and the upper part of the pipe and the upper part of the plug were sealed by welding (
Comparative example 1), a stainless steel plug body without a flange is inserted into a stainless steel pipe, and the pipe portion protruding from the lid body is caulked to form an annular constriction toward the internal plug body. Prepare 20 batteries (comparative example 2) each manufactured by sealing the surface and the outer peripheral surface of the plug and sealing the upper part of the pipe and the upper part of the plug by welding. The occurrence of pinholes was tested.The test was conducted by dropping a silver nitrate solution, which is a chloride ion detection indicator, onto the welded part and measuring the number of pieces that showed white coloration.As a result, the comparison example 1 is 2
The occurrence of pinholes (white coloring) was observed in 1 A out of 00 batteries, and in Comparative Example 2, the occurrence of pinholes was observed in 3 out of 200 batteries. In contrast, in this example, no three pinholes were observed in all 200 pinholes.

In addition, in the above example, a plug body having a flange having the same diameter as the outside diameter of the pipe was used once a month, but the flange may be slightly smaller than the outside diameter of the pipe or slightly larger than the outside diameter of the pipe. Good too.

[Effects of the Invention] As described in detail above, according to the present invention, a flange is provided at the upper end of a metal pipe for liquid injection that also serves as a terminal of the other polarity and is liquid-tightly fixed to a metal lid via an insulating sealant. Insert a plug body to H, and caulk the pipe portion protruding from the lid body to form an annular constriction toward the internal plug body, so that the inner circumferential surface of the pipe and the outer circumferential surface of the plug body are intimately connected. Furthermore, by welding the upper end surface of the pipe to the flange of the stopper that comes into contact with it, the pipe can be sealed liquid-tightly, and the electrolyte inside the metal case will not leak out during use. We present a method for manufacturing non-aqueous solvent batteries with a sealed structure at a high yield (1%).

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a non-aqueous solvent battery manufactured according to an embodiment of the present invention, and FIG. 2 does not show the metal stopper used in manufacturing the non-aqueous solvent battery shown in FIG. It is a diagram. 1... Can body, 2... Negative electrode, 3... Positive electrode, 4a,
4b... Separator, 8... Lid, 10... Stainless steel pipe, 13... Electrolyte, 14... Flange, 15
... Plug body, 1B... Constriction. Applicant's agent Patent attorney Takehiko Suzue Figure 1 Figure 2

Claims (1)

[Claims] A process of storing a negative electrode made of a light metal and a positive electrode mainly composed of porous carbon in a metal case that also serves as a one-polar terminal via a separator, and a metal pipe that also serves as a terminal of another polarity is placed in a hole near the center in advance. A step of fitting a metal lid, which is liquid-tightly fixed via an insulating material so as to protrude from one end of the pipe, into the upper opening of the metal can and sealing it by welding, and passing the metal pipe through the metal can. accommodating an electrolytic solution containing an oxyhalide as a positive electrode active material in the metal can; inserting a metal stopper into the metal pipe; and the end of the metal pipe protruding from the lid and the stopper. In the manufacturing of a non-aqueous solvent battery, which includes a step of sealing the metal pipe by welding, a plug having a flange at the upper end is used, and the plug is inserted into the metal pipe to close the pipe. The flange is brought into contact with the upper end surface, and the pipe portion protruding from the metal lid is caulked to form an annular constriction toward the internal plug, thereby connecting the inner circumferential surface of the pipe and the plug. A method for manufacturing a non-aqueous solvent battery, comprising: bringing the outer peripheral surfaces into close contact with each other, and then welding and sealing the upper end surface of the pipe and the flange of the stopper that abuts the upper end surface of the pipe.