JPH07320704A - Cylindrical manganese dry battery - Google Patents

Abstract

PURPOSE:To provide such a cylindrical manganese dry battery as being excellent in leakage resistance and storage performance by promptly releasing gas pro duced in the battery during discharge to the outside and preventing the entry of oxygen gas in the atmosphere to the inside during storage. CONSTITUTION:A synthetic resin sealing 6 formed by inserting a carbon rod 4 into a transparent hole 61 at the center is arranged at the opening of a negative electrode zinc can 2 in which positive electrode composite agent 1 and a separator 3 are contained, and thrusted and fixed against the opening end 21 of the negative electrode zinc can 2 with a metal jacket 10 via the upper end of a resin tube 7, the outer periphery of a positive electrode terminal plate 8 and an insulating ring 9. The inner diameter of the transparent hole 61 in the sealing 6 is larger than the outer diameter of the carbon rod 4 and at least one annular membrane valve 6a with the inner diameter being smaller than the outer diameter of the carbon rod 4 is provided on the inner periphery of the transparent hole 61 in the sealing 6. The membrane valve 6a is preferably provided with high-viscosity oily fluid layer 14.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cylindrical manganese dry battery, and more specifically, it quickly discharges gas generated inside the battery to the outside of the battery during discharge and oxygen in the atmosphere during storage. The present invention relates to a cylindrical manganese dry battery that prevents gas from entering the inside of the battery, has excellent liquid leakage resistance, and has good storage performance.

[0002]

2. Description of the Related Art Conventionally, in a manganese dry battery, mercury is dissolved in an electrolytic solution and zinc is amalgamated with mercury to prevent zinc corrosion, or zinc is alloyed with cadmium to prevent zinc corrosion. Therefore, the discharge performance has been improved.

In such a manganese dry battery containing mercury or cadmium, zinc was uniformly dissolved in the electrolytic solution by the action of mercury or cadmium at the time of discharge, and the generation of gas during discharge was suppressed. From the viewpoint of pollution prevention, harmful substances such as mercury and cadmium cannot be used, and as a result, zinc is not dissolved in the electrolyte solution uniformly, and due to discharge, hydrogen gas is generated from the uneven part. There is a problem that the generated gas causes leakage of the electrolyte solution.

Therefore, most of the cylindrical manganese dry batteries so far have been designed to prevent leakage of the electrolytic solution by enclosing the gas generated during the discharge inside the battery.

However, when the negative electrode zinc can is consumed by the discharge and a hole is formed in the negative electrode zinc can, and the gas contained in the battery is ejected from the hole of the negative electrode zinc can to the outside of the battery, electrolysis is accompanied with it. Liquid also spouts outside the battery,
There was a problem that the electrolyte leaked out.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the problem that the conventional cylindrical manganese dry battery has a problem that the electrolytic solution leaks out due to the gas generation during discharging, and occurs inside the battery during discharging. An object of the present invention is to provide a cylindrical manganese dry battery that releases gas rapidly to the outside of the battery and prevents oxygen in the atmosphere from entering the inside of the battery, has excellent leakage resistance and good storage performance. .

[0007]

The structure of the present invention for solving the above-mentioned problems will be described with reference to FIGS. 1 to 3 corresponding to the embodiment. The inner diameter is made larger than the outer diameter of the carbon rod 4, and the through hole 61 of the sealing body 6 is formed.
An annular membrane valve 6a having an inner diameter smaller than the outer diameter of the carbon rod 4 is provided on the inner peripheral side of the. Further, preferably, the membrane valve 6a has a vertical cross-section, and the highly viscous oily fluid layer 14 is disposed on the positive electrode terminal plate 8 side of the membrane valve 6a.

In the cylindrical manganese dry battery of the present invention having the above structure, since the membrane valve 6a is provided on the inner peripheral side of the through hole 61 of the sealing body 6, the sealing body 6 and the carbon rod 4 are provided with the above membrane valve 6a. Contact only at.

Therefore, when gas is generated inside the battery, the membrane valve 6a is pushed up by the pressure and the sealing body 6 is closed.
A gap is formed between the inner peripheral surface of the through hole 61 and the outer peripheral surface of the carbon rod 4, and the gas inside the battery passes through the above gap, and further passes between the positive electrode terminal plate 8 and the resin tube 7. And then released to the outside of the battery.

When the pressure inside the battery becomes lower than the atmospheric pressure, the tip of the membrane valve 6a descends and comes into contact with the outer peripheral surface of the carbon rod 4 again, so that oxygen in the atmosphere may enter the inside of the battery. To be prevented. Therefore, oxygen in the atmosphere is prevented from entering the inside of the battery and reacting with the active material to cause self-discharge, and as a result, good storage performance is maintained.

The shape of the membrane valve 6a is not particularly limited as long as it has the above-mentioned action, but as shown in the drawing, when the positive electrode terminal plate 8 side is placed on the upper side, the vertical cross-sectional shape thereof is The V-shape is suitable for performing the above-mentioned action and is preferable. However, since the inner diameter of the membrane valve 6a is smaller than the outer diameter of the carbon rod 4, when the carbon rod 4 is inserted into the through hole 61 of the sealing body 6 from below, the inner peripheral side portion of the membrane valve 6a is pushed up. However, since the membrane valve 6a has a vertical cross-sectional shape, the membrane valve 6a does not necessarily have to have the V-shape from the beginning.

To prevent the invasion of oxygen from the outside of the battery, a highly viscous oily fluid layer 14 is provided on the positive electrode terminal plate 8 side of the membrane valve 6a (that is, the outlet side of the gas inside the battery to the outside of the battery). By installing it, the effect can be enhanced.

When the oily fluid layer 14 is arranged as described above, the pressure inside the battery for preventing oxygen from entering and the gas release rate inside the battery can be adjusted by the viscosity of the oily fluid layer 14. is there.

However, since the gas generation rate of the battery internal pressure and the gas release rate differs depending on the discharge condition and the power generation element, it is difficult to determine a suitable viscosity range of the oily fluid layer 14, and it is actually used. Since it is difficult to measure the viscosity of the oily fluid, it is practically suitable to judge the viscosity by the viscosity of the material forming the oily fluid layer 14.

Examples of the highly viscous oily fluid for forming the oily fluid layer 14 include polybutene, pitch, and
Wax or the like is used.

At least one membrane valve 6a may be provided, but it is preferable to provide a plurality of membrane valves 6a if possible. Although the size of the membrane valve 6a varies depending on the hardness of the material of the sealing body 6, when the sealing body 6 is made of low density polyethylene,
The film thickness is a uniform thickness of 0.1 to 0.3 mm, or has a taper shape in which the thickness gradually decreases toward the tip (that is, the inner circumference side), and the width in the inner circumference direction is the outer circumference of the carbon rod 4. 1.2 of the gap between the surface and the inner peripheral surface of the through hole 61 of the sealing body 6.
It is preferably about 2 times.

[0017]

Embodiments of the present invention will now be described with reference to the drawings. However, the present invention is not limited to the examples illustrated in the embodiments, and the materials of each component are not limited to those illustrated.

FIG. 1 is a partial sectional view showing an embodiment of the cylindrical manganese dry battery of the present invention, and FIG. 2 is an enlarged sectional view showing a sealing body used in the battery shown in FIG. 3 is an enlarged cross-sectional view of a main part of the battery shown in FIG. It should be noted that in the cross-sectional portion of the battery shown in FIG. 1 and FIG. 3, the portion on the back side of the cut surface is rather complicated, so that only the cut surface is shown.

In the figure, 1 is a positive electrode mixture, 2 is a negative electrode zinc can, 3
Is a separator, 4 is a carbon rod, 5 is a cover paper, 6 is a sealing body,
7 is a resin tube, 8 is a positive terminal plate, 9 is an insulating ring,
10 is a metal jacket, 11 is a negative electrode terminal plate, 12 is an insulating packing, 13 is a bottom paper, and 14 is a highly viscous oily fluid layer.

The positive electrode mixture 1 is made of a powder prepared by mixing manganese dioxide, acetylene black and an electrolytic solution, and the negative electrode zinc can 2 is made of a metal zinc molded into a cup shape. The positive electrode mixture 1 and the separator 3 are filled in the inside thereof.

The separator 3 is made of kraft paper with one side coated with a sizing material containing processed starch as a main material. The separator 3 is arranged so that the sizing material coated surface faces the negative electrode zinc can 2. The positive electrode mixture 1 and the negative electrode zinc can 2 are separated from each other.

The carbon rod 4 is made by solidifying carbon powder, and the lower portion thereof has the through hole 61 of the sealing body 6 and the upper lid paper 5.
Of the positive electrode mixture 1, the lower end thereof reaches the vicinity of the lowermost part of the positive electrode mixture 1, and the upper part thereof is in contact with the positive electrode terminal plate 8 to act as a current collector on the positive electrode side.

The sealing body 6 is formed by molding a polyolefin resin such as polyethylene or polypropylene or nylon, and has a through hole 61 into which the carbon rod 4 is inserted, as shown in FIG. On the inner peripheral side of the through hole 61, a ring-shaped membrane valve 6a having a vertical cross-section is provided.

The size of the annular membrane valve 6a is the same as the sealing body 6.
When the sealing body 6 is made of low-density polyethylene, the film thickness is 0.1 to 0.1, although it depends on the hardness of the material.
It is preferable that the thickness is 0.3 mm or a taper shape, and the width in the inner peripheral direction is about 1.2 to 2 times the gap between the outer peripheral surface of the carbon rod 4 and the inner peripheral surface of the through hole 61 of the sealing body 6.

The sealing body 6 exemplified in this embodiment is made of low density polyethylene, and the membrane valve 6a has a uniform thickness of 0.2 mm, the outer diameter of the carbon rod 4 is 8 mm, and the sealing body 6 is transparent. Hole 61
Has an inner diameter of 9 mm, the inner diameter of the membrane valve 6a is 7.5 mm, and the width in the inner circumferential direction is 0.75 mm. The inner circumferential width of this membrane valve 6a is the outer circumferential surface of the carbon rod 4 and the sealing. Through hole 6 in body 6
1 is 1.5 times the gap between the inner peripheral surface and the inner peripheral surface. And
In the present embodiment, the membrane valve 6a is divided into upper and lower two stages (that is, 2
It is provided).

The high-viscosity oily fluid layer 14 is formed by heating polybutene, pitch, wax, etc. and melting it, and the melted material is provided on the inner peripheral side of the through hole 61 of the sealing body 6 to form an annular membrane valve 6.
It is formed by pouring it on a and cooling it, and is made of polybutene in this embodiment.

The upper lid paper 5 is formed by punching a paperboard in an annular shape having a central hole, and the resin tube 7 is formed of a heat-shrinkable resin film.
Is arranged on the outer peripheral side, and the upper end covers the outer peripheral upper surface of the sealing body 6, and the lower end covers the lower surface of the insulating packing 12.

The positive electrode terminal plate 8 is made of a tin plate, and its central portion has a cap shape for covering the upper end portion of the carbon rod 4, and its outer peripheral portion has a flat plate shape. The insulating ring 9 is made by punching a vinyl chloride resin plate into a ring shape,
The positive electrode terminal plate 8 is arranged on the flat outer peripheral portion. The bottom paper 13 is formed by punching a paper board in a circular shape and is arranged on the inner surface side of the bottom of the negative electrode zinc can 2.

The negative electrode terminal plate 11 is made of a tin plate, and the outer peripheral portion thereof has a flat plate shape. The insulating packing 12 is formed by punching a paraffin-impregnated paperboard in a ring shape, and is arranged in contact with the outer surface side (lower side in the figure) of the flat plate-shaped outer peripheral portion of the negative electrode terminal plate 11.

The metal jacket 10 is formed by rolling a tin plate into a tubular shape, is arranged on the outer peripheral side of the resin tube 7, has its lower end bent inward, and its upper end curled inward. The tip of the insulating ring 9 contacts the insulating ring 9, the outer peripheral portion of the positive electrode terminal plate 8, the upper end portion of the resin tube 7, the outer peripheral portion of the sealing body 6, the open end portion 21 of the negative electrode zinc can 2, and the resin tube 7. The lower end portion, the insulating packing 12, and the negative electrode terminal plate 11 are pressed in the axial direction to fix them to predetermined positions. Further, usually, design printing is applied to the outer peripheral surface of the cylindrical portion of the metal jacket 10.

Next, the amount of the gas generated by the 10 Ω continuous discharge of the battery of the above-mentioned embodiment and the battery of the conventional structure shown in FIG. 4 (battery of the conventional example) released to the outside of the battery and the liquid leakage property during the 10 Ω continuous discharge. I checked. Further, the discharge performance of the battery of the above-mentioned example and the battery of the conventional structure shown in FIG. 4 after being stored at room temperature for 1 year and 2 years was examined. In the battery having the conventional structure shown in FIG. 4, the inner diameter of the through hole of the sealing body 6 is 8 mm, the inner peripheral surface is entirely in contact with the outer peripheral surface of the carbon rod 4, and the membrane valve 6a is It is a cylindrical manganese dry battery having the same configuration as the battery of the embodiment except that it is not provided or the highly viscous oily fluid layer 14 is not provided.

Each battery had an outer diameter of 34 mm and a total height of 61.
It is a 5 mm R20 type cylindrical manganese dry battery, and the amount of gas released to the outside of the battery was measured by measuring 20 of each of the two batteries.
It was carried out by continuously discharging at a temperature of 10 Ω for a predetermined period, introducing gas released from the battery into liquid paraffin, and measuring the amount of accumulated gas. In Table 1, one day after the start of discharge,
The accumulated gas amount after 2 days, 3 days, and 4 days is shown as the gas release amount.

The leak test was carried out at 20 ° C. for each of two batteries at 20 ° C.
It was carried out by discharging at 0Ω for a predetermined period to examine whether or not electrolyte leakage occurred. In Table 2, 3 days, 5 days, 10 days, 20 days, 40 days and 80 days after the start of discharge.
The number of leak-generating batteries after a day is shown. However, in Table 2, the number of leaked batteries is shown in a mode in which the number of batteries used in the test is used as a denominator and the number of leaked batteries is shown in the numerator.

Regarding the discharge performance after storage, both batteries after storage for 1 year and 2 years had a final voltage of 0.
The discharge duration was measured by continuously discharging to 9 V, and an index was obtained with the discharge duration immediately after assembly as 100. The results are shown in Table 3. The discharge duration of the battery immediately after assembly was 56 hours in both the example and the conventional example. In addition, Table 1
In Table 3, the battery having the conventional structure shown in FIG. 4 is simplified and referred to as “conventional example”.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

As is clear from the results shown in Table 1, in the battery of the example of the present invention, the gas generated inside the battery could be discharged to the outside of the battery from the first day after the start of discharge. In the battery of the conventional example, gas was released from the third day. In this way, in the battery of the conventional example, the reason why the gas was released from the third day is considered to be that there was a hole in the negative electrode zinc can on the third day from the start of the discharge.

Further, as is clear from the results shown in Table 2, the batteries of the examples of the present invention had no leakage of the electrolytic solution and were excellent in the leakage resistance as compared with the batteries of the conventional example.

As shown in Table 3, the batteries of the examples of the present invention have the same discharge performance after storage as the batteries of the conventional example, the invasion of oxygen in the atmosphere is prevented, and the membrane valve 6a. No significant decrease in discharge performance due to contact with the carbon rod 4 was observed, and the storage performance was good.

[0041]

As described above, according to the present invention, the gas generated inside the battery due to discharge can be quickly released to the outside of the battery, and oxygen in the atmosphere can be prevented from entering the inside of the battery. It was possible to provide a cylindrical manganese dry battery having excellent liquid leakage resistance and good storage performance.

That is, in the cylindrical manganese dry battery of the present invention, the annular membrane valve 6a provided on the inner peripheral side of the through hole 61 of the sealing body 6 causes the gas generated inside the battery due to the discharge to the outside of the battery. Since the gas pressure inside the battery is kept low at all times because the gas is discharged gradually, even if there is a hole in the negative electrode zinc can 2 as a result of discharging, the gas does not blow out to the outside of the battery. It does not leak to and has excellent leakage resistance. Further, since the membrane valve 6a prevents the oxygen in the atmosphere from entering the inside of the battery, the deterioration of the discharge performance due to storage is suppressed and the storage performance is also good.

[Brief description of drawings]

FIG. 1 is a partial sectional view showing an embodiment of a cylindrical manganese dry battery of the present invention.

FIG. 2 is an enlarged cross-sectional view of a sealing body used in the battery shown in FIG.

FIG. 3 is an enlarged cross-sectional view of a main part of the battery shown in FIG.

FIG. 4 is a partial cross-sectional view showing a conventional cylindrical manganese dry battery.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode mixture 2 Negative electrode zinc can 3 Separator 4 Carbon rod 6 Sealing body 61 Through hole 6a Membrane valve 7 Resin tube 8 Positive electrode terminal plate 9 Insulation ring 10 Metal jacket 14 Oily fluid layer

Claims (3)

[Claims] 1. A synthetic resin sealing body 6 in which a carbon rod 4 is inserted into a through hole 61 in a central portion is provided at an opening portion of a negative electrode zinc can 2 accommodating a positive electrode mixture 1 and a separator 3, In a cylindrical manganese dry battery in which the sealing body 6 is pressed and fixed to the open end 21 of the negative electrode zinc can 2 with the metal jacket 10 via the upper end of the tube 7, the outer periphery of the positive electrode terminal plate 8 and the insulating ring 9. The inner diameter of the through hole 61 of the sealing body 6 is made larger than the outer diameter of the carbon rod 4, and an annular membrane valve 6a having an inner diameter smaller than the outer diameter of the carbon rod 4 on the inner peripheral side of the through hole 61 of the sealing body 6. A cylindrical manganese dry battery, characterized in that at least one or more are provided. 2. The vertical cross-sectional shape of the membrane valve 6a provided on the inner peripheral side of the through hole 61 of the sealing body 6 is a V-shape when the positive electrode terminal plate 8 side is facing upward. Cylindrical manganese battery. 3. The cylindrical manganese dry battery according to claim 1, wherein a highly viscous oily fluid layer 14 is disposed on the positive electrode terminal plate 8 side of the membrane valve 6a provided on the inner peripheral side of the through hole 61 of the sealing body 6. .