JPS6038825B2 - dry battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improving the sealing part of dry batteries such as alkaline manganese batteries, nickel cadmium batteries, and Leclanche type dry batteries, and aims to improve leakage resistance.

The open end of the battery container containing the power generation element is bent halfway inward, and a synthetic resin gasket and a sealing plate that also serves as a terminal are attached to the closed end to create a competitive exterior on the outside of the battery container. In a dry battery, the open □ end of the battery container bites into the gasket by tightening the can, and the biting part locally prevents the electrolyte from leaking to the outside along the surface of the battery case. In order to further improve the liquid tightness of the battery case, or because there is a concern that the open edges of the battery container may become rounded and high liquid tightness cannot be obtained at the biting part, we use asphalt pitch, anti-greasy polyamide resin, and low polymerization degree. It has been proposed that the open end of the battery container be fitted into a gasket using a sealant such as fluororesin or polyisobutylene.

However, with the sealant described above, the coating is relatively hard and it is not possible to seal the minute gap between the end of the battery container and the gasket. The elasticity and water repellency of the sealant may deteriorate due to low-temperature thermal history, and when the open end of the battery container is inserted into the gasket through the sealant coating, the sealant coating may be damaged. There are various drawbacks such as breakage due to rough edges, and the effect of using a sealant cannot be fully demonstrated.

The present invention provides a dry battery having a structure in which a gasket is brought into contact with the closed end of the battery container, and the closing end of the battery container is bitten into the gasket by tightening the outer can that is pressed against the outside of the battery container. A dry battery having a high liquid-tight effect is provided by making the opening device of the battery container bite into the gasket via a sealant made of a phosphanzene polymer containing hydrogen.

Further, in a preferred embodiment of the present invention, the open end of the battery container is bitten into the gasket through a sealant made of a phosphanzene polymer having a fluorinated hydrocarbon in its side chain and not having a crosslinked structure. The present invention provides a dry battery having even higher liquid-tightness.

In another preferred embodiment of the present invention, the open end of the battery container is bitten into a gasket through a sealant made of a phosphanzene polymer having a repeating unit represented by the following general formula, thereby achieving even higher liquid tightness. The present invention provides a dry battery having the following characteristics.

General formula However, R in the formula is -C ratio (CF2)aCF3, R' is -
CH2 (a -valent group selected from the group CF2>bH, where a and b are integers between 0 and 9);

Phosphazene is a compound in which nitrogen and phosphorus bonds are arranged alternately as a skeleton. Phosphorus pentachloride is dissolved in an organic solvent such as tetrachloroethane, chlorobenzole, or nitrobenzole, and ammonium chloride is mixed with this. A crystalline substance obtained by the reaction is represented by (PNCI)m (where m is an integer of 3 or 4), and when m is 3, it has a cyclic structure as shown in '1} below. When heated, it easily undergoes ring-opening polymerization to form a polymer compound as shown in (■) below, which has rubber elasticity. However, the bond between phosphorus and chlorine in the formula is extremely unstable, and it absorbs moisture in the air. Because it absorbs moisture and hydrolyzes, it is unsuitable as a sealant for dry batteries. Therefore, in the present invention, the compound [21], for example, CF30Na, CF3CQONa, HC2
F4C string ○Na, HC3F6CH20Na, C6 ratio F
A phosphanzene polymer having a fluorinated hydrocarbon in the side chain, obtained by reacting one or more types of fluorinated alkoxides such as OK, C6, 4CF30K, is used as a sealing agent, and its structure An example of the formula is as follows. Phosphanzene polymers with fluorinated hydrocarbons in their side chains have a high elongation rate and good elasticity, so when the closed end of the battery container is inserted into the gasket, the sealant coating interposed between them is easily removed. Because it does not break due to the open □ end and fits well into minute recesses formed on the surface of the battery container, etc., due to the local bite of the open □ end and the elasticity of the sealant at the biting part, Leakage of electrolyte solution can be effectively prevented.

Furthermore, the phosphanzene polymer of the present invention shows no deterioration at all even when immersed in a highly concentrated alkaline solution or an electrolytic solution such as a mixed solution of zinc chloride and ammonium chloride for a long period of time, and is chemically extremely stable. Since there is no deterioration in physical properties such as elasticity and water resistance even after repeated thermal history up to high temperatures, the above-mentioned excellent leakage prevention effect can be stably obtained over a long period of time. Organic peroxides such as diacyl/g-oxide, ketone/g-oxide, alkyl/g-oxide, dialkyl/g-oxide, peroxycarbonate, etc. By reacting one or more types of tyronitrile, a high molecular weight polymer having a crosslinked structure can be obtained. Phosphanzene polymer with this crosslinked structure has good moldability, so it can be made into a thin sheet and sealed.
However, when cross-linking reaction occurs, the elasticity and elongation of the phosphanzene polymer tend to decrease. Using a phosphasozene polymer as a sealant, which is not included, has better adhesion to the sealing plate and gasket, and better solubility in solvents. Organic liquids such as ketones, tetrahydrofuran, and esters are used as solvents for the phosphinzenpo IJ mer according to the present invention. Among the phosphanzene polymers according to the present invention, a polymer having a repeating unit represented by the following general formula is particularly useful because it has extremely high rubber elasticity.

General formula However, R in the formula is -C ratio (CF2)aCF3, R' is -
A monovalent group selected from the group CF2)bH, where a and b are integers between 0 and 9.

Rather than symmetrically adding the same fluorinated hydrocarbons to the side chains of the phosphanzene polymer, it is better to add different hydrocarbons to the side chains as in the general formula above, and the above a and b are An integer that does not exceed 9 has better rubber elasticity than a phosphanzene polymer in which the same fluorinated hydrocarbon is symmetrically added to the side chain, and a phosphanzene polymer in which a and b exceed 10. . Next, an embodiment of the present invention will be described with reference to FIG.

An anode mixture 3 made of a mixture of manganese dioxide, acetylene black, and zinc chloride-ammonium chloride electrolyte is introduced into the battery container 1 made of a zinc can through a separator 2 coated with a glue such as starch. The carbon rod 4 is loaded, the open □ end 5 of the battery container 1 is bent halfway inward, and a liquid in which the phosphanzene polymer according to the present invention is dissolved in an organic solvent is poured from the inner surface to the outer surface of the open □ end 5. It is applied and dried to form a continuous sealant coating 6. A gasket 8 made of synthetic resin such as polyethylene or polypropylene, which has a through hole 7 in the center through which the carbon rod 4 passes, is attached to the carbon rod 4, and the gasket 5 is attached to the open end 5 of the battery container 1.
Support the bottom of 8. A cathode terminal plate 9 is attached to the bottom surface of the battery container 1.
A resin tube 10 made of heat-shrinkable polyvinyl chloride or the like is attached to the outside of the battery container 1, and the upper end of the resin tube 10 is placed along the upper periphery of the gasket 8, while the lower end is connected to the insulating ring 11. are bent inwardly along the lower circumferential edge of the cathode terminal plate 9 through the holes. Next, the anode terminal plate 12
is placed on top of the gasket 8, and the upper end 14 of the metal outer can 13 iron-bonded to the outside of the battery container 1 via the resin tube 10 is curled inward to utilize the tightening force of the outer can 13. Then, the upper end of the resin tube 10 is crimped onto the upper surface of the gasket 8, and the closed end 5 of the battery container 1 is bitten into the gasket 8 via the sealant coating 6, completing the assembly of the Leclanche type dry battery. FIGS. 2 and 3 show an example of an alkaline manganese battery, in which inside a battery container 21 made of a nickel-plated iron can,
An anode mixture 22 made by pressure-molding a mixture of manganese dioxide and phosphorous graphite into a cylindrical shape is inserted, and an amalgam is inserted into the hollow part of the anode mixture 22 through a separator 23 made of pinylon-rayon paper. The battery container 21 is filled with a cathode agent 24 made of a kneaded mixture of a gel agent made of zinc powder and polyacrylate, and an alkaline electrolyte, and the open square end 25 of the battery container 21 is bent halfway inward.

A gasket 26 made of polyethylene, polypropylene, polyamide, etc. is provided with a through hole 28 in the center thereof into which a current collector 27 is fitted, and an annular groove 29 in a position facing the open □ end 25 of the battery container 21. , the annular groove 2
When a liquid obtained by dissolving the phosphanzene polymer according to the present invention in an organic solvent is poured into the groove 9 and dried, a coating 30 containing a large amount of sealant is formed at the bottom of the annular groove 29 as shown in FIG.

The current collector 27 with the cathode terminal plate 31 fixed to the end face is inserted into the through hole of the gasket 26, and the gasket 26 and the current collector 2
7 and the current collector of the cathode terminal plate 31 are inserted into the battery container 21 with the tip of the current collector 27 facing down, and the open □ end 25 of the battery container 21 is inserted.
is fitted into the annular groove 29 of the gasket 26. Next, a resin tube 32 made of heat-shrinkable polyvinyl chloride is attached to the outside of the battery container 21, and a metal outer can 33 is iron-fitted to the resin tube 32, so that the lower end of the outer can 33 is turned inward. Tighten, and the open end 25 of the battery container 21 is tightened with the tightening force.
into the gasket 26 through the sealant coating 30. In the method of applying a sealant solution to the closed end of the battery container, there is a concern that the sealant drips down during drying, reducing the amount of sealant attached to the edge of the open end. If an annular groove is provided on the surface of the gasket facing the entrance end of the battery container and a sealant is poured into the annular groove to form a coating, the effect of the sealant can be reliably exerted with a small amount.

The leakage rate when the alkaline manganese battery of the present invention shown in FIG. 2 and a battery of the same type using a conventional sealant were stored at 35° C. and 80% relative humidity are shown below.

Table: Leakage rate (Unit) The present invention has the above-mentioned structure, and a stable sealing effect can be achieved for a long period of time at the part where the open end of the battery container is bitten into the gasket. Since the electrolytic solution that attempts to leak out through the surface is locally blocked by the biting portion, excellent leakage resistance can be obtained as is clear from the table above.

It has been experimentally confirmed that other sealants belonging to the present invention not listed in the above table can also provide similar excellent leakage resistance in the case of Leclanche type dry batteries.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a main part of a Leclanchier dry battery according to an embodiment of the present invention, FIG. 2 is a cross-sectional view of a main part of an alkaline manganese battery according to another embodiment of the present invention, and FIG. FIG. 2 is a sectional view of main parts showing an assembled state of the battery. 1, 21... Battery container, 5, 25...
Closed end, 6, 30... Covered, 8, 26...
...Gasket, 13,33...Exterior can. Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. In a dry battery having a structure in which a gasket is brought into contact with the open end of the battery container, and the outer can fitted on the outside of the battery container is tightened, the open end of the battery container is bitten into the gasket. 1. A dry battery characterized in that an open end of a battery container is wedged into a gasket via a sealant made of a phosphanzene polymer containing fluorinated hydrocarbons. 2. The dry battery according to claim 1, wherein the sealant is a phosphazene polymer having a fluorinated hydrocarbon in its side chain and not having a crosslinked structure. 3. The dry battery according to claim 1, wherein the sealant is a phosphazene polymer having a repeating unit represented by the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R in the formula is -CH_2(CF_2)aCF_3,
R' is a monovalent group selected from the group -CH_2(CF_2)bH, and a and b are integers between 0 and 9.