JP2937353B2 - Zinc chloride dry cell - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a zinc chloride type dry battery, and more particularly, to a zinc chloride type dry battery having a large discharge capacity and a small decrease in discharge performance during storage.

[Conventional technology]

A zinc chloride type dry battery is an electrolyte using manganese dioxide as a positive electrode active material, acetylene black as a conductive additive, and zinc chloride as a main electrolyte (so-called zinc chloride type electrolyte).
Is used.

This zinc chloride type dry battery has advantages such as a larger discharge capacity at a large current discharge and less liquid leakage than a dry battery using ammonium chloride as a main electrolyte.

However, in this zinc chloride type dry battery as well, demands for downsizing and higher performance of the battery-using equipment require higher discharge performance.

Therefore, first, the current state of the zinc chloride type dry battery manufactured by the present applicant is described. The use ratio of acetylene black (AB) to manganese dioxide (MnO ₂ ) in the positive electrode mixture (AB / MnO ₂ ) is expressed by weight. AB / MnO ₂ = 16.13 / 100.

The composition of the electrolytic solution showing the best performance in the use ratio of acetylene black to the manganese dioxide, that is, the ratio of zinc chloride (ZnCl ₂ ) to the amount of manganese dioxide (MnO ₂ ) in the electrolytic solution (ZnCl ₂ / MnO ₂ ) Is Zn in weight ratio
Cl ₂ / MnO ₂ = 0.203, and the water (H
₂ O) to manganese dioxide (MnO ₂ ) (H ₂ O / Mn
O ₂ ) is H ₂ O / MnO ₂ = 0.529 in weight ratio, and in the SUM-1 type battery, the filling amount of manganese dioxide in the battery is 30.8 g.
The discharge duration in 2Ω continuous discharge is 370 minutes, and the discharge duration in 2Ω intermittent discharge is 560 minutes.

Therefore, in order to meet the above-mentioned demands from the equipment using the battery, if the discharge capacity of this zinc chloride type dry battery is increased, the discharge utilization rate of manganese dioxide is almost determined by the load. It is difficult to increase the rate, and the actual situation is that the amount of manganese dioxide in the positive electrode active material must be increased.

[Problems to be solved by the invention]

However, since the positive electrode mixture that can be charged in the battery is almost constant, when the amount of manganese dioxide is increased, the amount of acetylene black must be reduced accordingly, and with the decrease of acetylene black, the positive electrode mixture is maintained. The hydraulic power decreases, and it is not possible to hold an amount of electrolyte required for discharge, and therefore, the discharge utilization rate of manganese dioxide decreases, and a sufficient discharge capacity cannot be obtained, and the discharge performance due to storage is reduced. There is a problem that the drop is large and liquid leakage is likely to occur.

Accordingly, an object of the present invention is to provide a zinc chloride type dry battery having a large discharge capacity and a small decrease in discharge performance due to storage.

[Means for solving the problem]

The present invention uses a manganese dioxide containing 20 to 40% by weight of fine manganese dioxide having a particle size of 1 to 10 μm in a range of 90% by weight or more as a positive electrode active material, and has an iodine adsorption amount of 250 to 319 mg / g.
Acetylene black containing 5% by weight or more of fine powder of acetylene black is used as a conductive assistant, and the amount ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is Zn in weight ratio.
By using Cl ₂ / MnO ₂ = 0.210~0.273 high concentration of zinc chloride type electrolyte is one in which has achieved the above objects.

That is, the conventionally used acetylene black has an iodine adsorption amount of about 80 to 100 mg / g.In the present invention, however, the particle diameter is smaller than such a conventionally used acetylene black, and the iodine adsorption amount is 250 to 310 mg / g. Acetylene black having a large surface area. Since the fine powder acetylene black has a large surface area and a large liquid absorption, the use of the fine powder acetylene black improves the electrolytic solution holding power of the positive electrode mixture. As a result, even when the amount of manganese dioxide in the positive electrode mixture is increased and the amount of acetylene black is reduced, the required amount of electrolyte solution for the positive electrode mixture can be maintained, the discharge utilization rate of manganese dioxide is improved, and The decrease in discharge performance due to storage is also reduced. In addition, the use of this fine powder of acetylene black increases the number of contact points between acetylene black and manganese dioxide, and increases the current collecting ability, thereby increasing the reactivity of manganese dioxide. The utilization rate improves.

In addition, in the present invention, 90% by weight or more of manganese dioxide of the positive electrode active material uses fine powdered manganese dioxide in the range of 1 to 10 μm to increase the electrolytic solution holding power of the positive electrode active material itself. In addition, the reactivity of the positive electrode active material is increased, and the discharge utilization rate of manganese dioxide during heavy load discharge is increased.

That is, the conventionally used manganese dioxide has a particle size of 20 to
Although it is about 80 μm, in comparison with this, the fine powdered manganese dioxide has a small particle size and a large surface area,
High retention of electrolyte.

In the past, instead of using fine powdered manganese dioxide, manganese dioxide with a particle size of about 20 to 80 μm was used,
This is because, when manganese dioxide is finely powdered, the bulk density is reduced, the amount of manganese dioxide that can be filled in the battery is reduced, and the discharge capacity may be reduced.

Therefore, in the present invention, 90% by weight or more has a particle size of 1 to 10 μm.
The use of fine powdered manganese dioxide in the range of 20 to 40% by weight of the total manganese dioxide as the positive electrode active material without causing any drawbacks caused by the use of the fine powdered manganese dioxide allows the electrolyte solution to be used. Taking advantage of the characteristic that the coercive force is large, the discharge utilization rate of the positive electrode active material particularly at the time of heavy load discharge is improved, which is useful for obtaining a battery having a large discharge capacity.

Further, in the present invention, as a result of increasing the use rate of manganese dioxide in the positive electrode mixture, the amount of zinc chloride with respect to manganese dioxide tends to be insufficient in the electrolyte solution having a composition conventionally used favorably. Use a concentrated electrolyte solution.

When this is represented by the weight ratio of zinc chloride (ZnCl ₂ ) in the electrolytic solution to manganese dioxide (MnO ₂ ) (ZnCl ₂ / MnO ₂ ), the weight ratio is ZnCl ₂ / MnO ₂ = 0.210 to 0.273, This is larger than the conventional ratio of zinc chloride to manganese dioxide in the electrolytic solution, ZnCl ₂ / MnO ₂ = 0.203, and the concentration of zinc chloride in the electrolytic solution is high. And, the amount ratio of zinc chloride to manganese dioxide in the electrolyte solution ZnCl ₂ / MnO ₂
= 0.210 to 0.273, when indicated by ratio of water (H ₂ O) in the electrolytic solution to manganese dioxide _{(MnO 2), H 2 O} / MnO 2 = 0.505~
It corresponds to 0.480.

In the present invention, by employing the above configuration, the usage ratio (AB / MnO ₂ ) of acetylene black and manganese dioxide in the positive electrode mixture can be reduced to, for example, about AB / MnO ₂ = 13.25 / 100. . That is, the usage ratio of acetylene black in the positive electrode mixture is reduced, and the usage ratio of manganese dioxide is increased, thereby improving the discharge capacity.

In the present invention, the iodine adsorption amount is 250 to 310 mg / g
May be used in an amount of 5% by weight or more of the total acetylene black used as a conductive additive. That is, when the ratio of the fine powdered acetylene black having an iodine adsorption amount of 250 to 310 mg / g in the total acetylene black is less than 5% by weight, the electrolytic solution holding power of the positive electrode mixture when the amount of manganese dioxide is increased. , The discharge utilization rate of manganese dioxide is reduced, and the discharge performance due to storage is reduced. On the other hand, the upper limit of the amount of the fine powdered acetylene black having an iodine adsorption amount of 250 to 310 mg / g is not particularly limited, and all the acetylene blacks as the conductive assistant may be the finely powdered acetylene black.

In the present invention, the iodine adsorption amount of the fine powder acetylene black used is specified to be 250 to 310 mg / g, because the iodine adsorption amount of the fine powder acetylene black is 250 mg / g.
This is because the holding power of the electrolytic solution does not have a great difference compared with the conventionally used acetylene black when it is smaller than g, and the surface area is large when the iodine adsorption amount of the fine powder acetylene black is larger than 310 mg / g. Therefore, it becomes active against manganese dioxide and is oxidized by manganese dioxide, so that the battery performance is greatly reduced.

In addition, since this fine powder acetylene black is bulky as compared with the conventionally used acetylene black, if it is used in the same weight as the conventionally used acetylene black, it becomes too bulky and causes a problem in the filling property. When powder acetylene black is used in place of conventional acetylene black, it is preferable to use about 60% of the weight of conventionally used acetylene black.

In the present invention, the fine manganese dioxide having 90% by weight or more in the range of the particle size of 1 to 10 μm is made into 20 to 40% by weight of the total manganese dioxide. If the proportion of the manganese dioxide is less than 20% by weight, the manganese dioxide's own electrolytic solution holding power is reduced, and particularly the discharge utilization rate of manganese dioxide during heavy load discharge is reduced. If the proportion of manganese dioxide in the total manganese dioxide is more than 40% by weight, the manganese dioxide becomes bulky and lacks filling properties, so that the amount of manganese dioxide that can be filled in the battery decreases and the discharge capacity decreases.

In the present invention, the weight ratio of zinc chloride (ZnCl ₂ / MnO ₂ ) in the electrolytic solution to manganese dioxide is changed to ZnCl ₂ by weight ratio.
₂ / MnO ₂ = 0.210 to 0.273, which is the above ZnCl ₂ / Mn
When O ₂ is smaller than 0.210, the amount of zinc chloride relative to manganese dioxide is insufficient, manganese dioxide is not effectively used for discharge, the discharge utilization rate of manganese dioxide is reduced, and the above ZnCl ₂ / MnO ₂ If it is larger than 0.273, water required for discharge cannot be secured, and the discharge does not easily proceed. That is, the discharge reaction of zinc chloride type batteries, the following reaction formula: _{8MnO 2 + 8H 2 O + ZnCl} 2 + 4Zn → 8MnOOH + ZnCl 2 · 4Zn (OH)
₂ and water is required for the discharge reaction. Therefore, as described above, when ZnCl ₂ / MnO ₂ increases and the concentration of zinc chloride in the electrolyte increases, the electrolyte (usually,
The electrolyte solution is composed of water, zinc chloride and ammonium chloride (usually about 10% of zinc chloride)], the amount of water in the electrolyte decreases, and the water required for discharge cannot be secured. .

〔Example〕

Next, the present invention will be described in more detail with reference to examples.

Example 1 120 parts by weight of finely powdered manganese dioxide having 90% by weight or more in the range of particle size of 0.1 to 10 μm, 280 parts by weight of manganese dioxide in the range of particle size of 20 to 80 μm, and iodine adsorption amount of 2 parts
A positive electrode mixture was prepared by mixing 3 parts by weight of fine powder of acetylene black of 80 mg / g, 50 parts by weight of acetylene black having 90 mg / g of iodine adsorption, and 187 parts by weight of an electrolytic solution having a zinc chloride concentration of 30% by weight. Prepared.

The positive electrode mixture was formed into a cylindrical shape using an extrusion molding base according to a conventional method, and inserted into a zinc can to assemble a zinc chloride dry battery having a structure shown in FIG. 1 in the form of SUM-1.

That is, the separator (2), the base paper (3) and the above-mentioned positive electrode mixture (4) are inserted into the zinc can (1), and after the electrolyte is injected, the top cover (5) is placed on the positive electrode mixture (4). ) Is placed, and after pre-pressing, the carbon rod (6) is inserted into the positive electrode mixture (4) through a through hole provided in the center of the top cover paper (5), and then the opening edge of the zinc can (1) is removed. After curling inward, a sealing body (7) having a light transmitting property at the center is fitted to a carbon rod (6), and a negative electrode terminal plate (8) is provided at the bottom of a zinc can (1).
After arranging a paper ring (9) on the periphery of the negative electrode terminal plate (8), a heat-shrinkable tube (10) made of vinyl chloride resin is arranged on the side surface of the zinc can (1), and heated to heat the heat-shrinkable tube. The shrinkable tube (10) is heat-shrinked, and the sealing body (7) located on the paper ring (9) arranged on the side of the zinc can (1) and the bottom of the zinc can (1) and on the top of the zinc can (1). ) Was covered.

Next, the positive electrode terminal plate (11) is fitted into the head of the carbon rod (6), and a resin ring (1) is attached to the outer peripheral edge of the positive electrode terminal plate (11).
After disposing 2), the components were tightened in the axial direction with a metal outer can (13), and the components were packaged to assemble a zinc chloride dry battery having the structure shown in FIG.

In the above zinc chloride type dry battery, the proportion of fine manganese dioxide (fine manganese dioxide in which 90% by weight or more is in the range of particle diameter of 1 to 10 μm) in the total manganese dioxide as the positive electrode active material accounts for 30% by weight. The proportion of fine acetylene black (fine acetylene black having an iodine adsorption amount of 280 mg / g) in all acetylene black as a conductive additive is 6% by weight.

The weight ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is ZnCl ₂ / MnO ₂ = 0.255, and the weight ratio of paper in the electrolyte to manganese dioxide (H ₂ O) /
MnO ₂ ) is H ₂ O / MnO ₂ = 0.500 in weight ratio, and the amount of the electrolyte solution injected into the battery is 25.0 g including that used in the preparation of the positive electrode mixture.

The use ratio of the total acetylene black and the total manganese dioxide in the positive electrode mixture (AB / MnO ₂₎ is, AB / MnO ₂ in a weight ratio of
= 13.25 / 100.

Comparative Example 1 280 parts by weight of manganese dioxide having a particle size in the range of 20 to 80 μm and acetylene black 45 having an iodine adsorption of 90 mg / g
Parts by weight and 135 parts by weight of an electrolytic solution having a zinc chloride concentration of 27% by weight to prepare a positive electrode mixture. A zinc chloride type dry battery having the same structure as that shown in FIG. 1 was produced.

The use ratio (AB / MnO ₂ ) of acetylene black and manganese dioxide in this battery is AB / MnO ₂ = 16.13 / by weight.
100 and the weight ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is ZnCl ₂ / MnO ₂ = 0.203 by weight.
And the ratio of the amount of water in the electrolyte to manganese dioxide (H ₂ O /
MnO ₂ ) is H ₂ O / MnO ₂ = 0.523 in weight ratio.

Comparative Example 2 400 parts by weight of manganese dioxide having a particle size of 20 to 80 μm, 53 parts by weight of acetylene black having an iodine adsorption of 90 mg / g, and 187 parts by weight of an electrolyte having a zinc chloride concentration of 30% by weight were mixed. A positive electrode mixture was prepared, and a zinc chloride type dry battery having the same structure as that shown in FIG. 1 was produced in the SUM-1 type in the same manner as in Example 1 except that this positive electrode mixture was used.

The use ratio (AB / MnO ₂ ) of acetylene black and manganese dioxide in this battery was AB / MnO ₂ = 13.75 in weight ratio.
And the weight ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is ZnCl ₂ / MnO ₂ = 0.225 by weight, and the weight ratio of water in the electrolyte to manganese dioxide (H _Two
O / MnO ₂ ) is H ₂ O / MnO ₂ = 0.500 by weight.

Comparative Example 3 120 parts by weight of finely powdered manganese dioxide containing 90% by weight or more of particles having a particle size of 0.1 to 10 μm, 280 parts by weight of manganese dioxide having a particle size of 20 to 80 μm, and an iodine adsorption amount of 9 parts
A positive electrode mixture was prepared by mixing 55 parts by weight of 0 mg / g acetylene black and 187 parts by weight of an electrolyte having a zinc chloride concentration of 30% by weight, and was the same as in Example 1 except that this positive electrode mixture was used. Thus, a zinc chloride type dry battery having the same structure as that shown in FIG.

The use ratio (AB / MnO ₂ ) of acetylene black and manganese dioxide in this battery was AB / MnO ₂ = 13.75 in weight ratio.
And the weight ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is ZnCl ₂ / MnO ₂ = 0.225 by weight, and the weight ratio of water in the electrolyte to manganese dioxide (H _Two
O / MnO ₂ ) is H ₂ O / MnO ₂ = 0.500 by weight.

For the battery of Example 1 and the batteries of Comparative Examples 1 to 3, initially and after storage at 45 ° C. for one battery, according to JIS C 8501, the discharge duration time when the battery was continuously discharged at a load of 2Ω and the battery intermittently at a load of 2Ω. The discharge duration when discharging was measured. Table 1 shows the results.

As shown in Table 1, the battery of Example 1 has a longer discharge duration at first and after storage than the battery of Comparative Example 1 corresponding to a conventional product, and has a larger discharge capacity even under heavy load discharge. It was showing that.

Also, the battery of Comparative Example 2 using the same manganese dioxide and acetylene black as the battery of Comparative Example 1 and increasing the use ratio of manganese dioxide in the positive electrode mixture has a low electrolyte solution holding power of the positive electrode mixture. In addition, the discharge utilization rate of manganese dioxide was reduced, the discharge duration was not increased, and the discharge duration was significantly reduced by storage. After storage, the discharge duration was shorter than that of the battery of Comparative Example 1.

Further, the battery of Comparative Example 3 in which fine manganese dioxide was used in the same ratio as the battery of Example 1 and acetylene black was not used was used, because the electrolyte holding power of the positive electrode mixture was small. The discharge duration was not as long as that of the battery of Example 1, and the discharge duration was significantly reduced by storage. After storage, the discharge duration was shorter than that of the battery of Comparative Example 1.

Examples 2-3 and Comparative Examples 4-6 Fine powdered manganese dioxide (90% by weight or more has a particle size of 1-10 μm)
m in the range of 10% by weight (Comparative Example 4), 20% by weight (Example 2), 40% by weight (Example 3), 50% by weight in the total manganese dioxide. A positive electrode mixture was prepared in the same manner as in Example 1 except that (Comparative Example 5) and 100% by weight (Comparative Example 6) were changed, and SUM was prepared in the same manner as in Example 1 except that these positive electrode mixtures were used. First in -1 form
A zinc chloride type dry battery having the same structure as that shown in the figure was produced.

The filling amount of the positive electrode mixture was 53.7 g in the battery of Example 1.
However, with the increase in the amount of the fine powdered manganese dioxide, the bulk density was reduced, the volume was increased, and those which could not be filled with 53.7 g were filled only as much as possible.

The batteries of Examples 2 to 3 and Comparative Examples 4 to 6 were initially discharged and stored at 45 ° C. for one month, and then discharged continuously according to JIS C 8501 at a load of 2Ω and intermittently at a load of 2Ω. The discharge time at the time of discharge was measured.

Table 2 shows the duration of the continuous discharge, and Table 3 shows the duration of the intermittent discharge. In Tables 2 and 3, the battery of Example 1 and the battery of Comparative Example 1 were prepared so that the change in the discharge duration due to the change in the ratio of the fine powdered manganese dioxide in the total manganese dioxide was easy to understand. The measurement results of the battery are also shown.

As shown in Tables 2-3, when the proportion of the fine powdered manganese dioxide in the total manganese dioxide reaches 20% by weight,
As can be seen from the battery of Example 2, both the continuous discharge and the intermittent discharge have a significantly longer discharge duration than the battery of Comparative Example 1. This is thought to be due to an increase in the use ratio of manganese dioxide in the positive electrode mixture based on the use of the fine powdered manganese dioxide, and an improvement in the discharge utilization rate of manganese dioxide due to an increase in the liquid retention capacity of the manganese dioxide itself. On the other hand, when the proportion of the fine powdered manganese dioxide in the total manganese dioxide was increased, the discharge duration of both continuous discharge and intermittent discharge was reduced up to 40% by weight in Comparative Example 1.
Although the battery of Comparative Example 5 has a remarkable difference from the battery of Comparative Example 1, the battery of Comparative Example 5 in which the amount of fine powdered manganese dioxide was increased to 50% by weight seems to be particularly close to the battery of Comparative Example 1 due to a shorter discharge time in continuous discharge. In the battery of Comparative Example 6 using the whole amount of fine powdered manganese dioxide, the discharge duration was
Battery is shorter.

Examples 4 to 5 Except that the ratio of the fine powdered acetylene black having an iodine adsorption amount of 280 mg / g in the total acetylene black was changed to 50% by weight (Example 4) and 100% by weight (Example 5), Examples were changed. 1 was prepared in the same manner as in Example 1 except that a positive electrode mixture was prepared and the positive electrode mixture was used.
A zinc chloride type dry battery having the same structure as that shown in the figure was produced.

For these batteries of Examples 4 to 5, initial and 45 ° C
After storage for 1 month, load 2 according to JIS C 8501
Discharge duration and load 2Ω when discharging continuously at Ω
The discharge time at the time of intermittent discharge was measured.

Table 4 shows the discharge duration during the continuous discharge, and Table 5 shows the discharge duration during the intermittent discharge. These fourth to fifth
In the table, the measurement results of the battery of Example 1 and the battery of Comparative Example 1 are also shown so that the change in the discharge duration with the change in the ratio of the fine powder acetylene black to the total acetylene black can be easily understood.

As shown in Tables 4 and 5, both the battery of Example 4 in which the amount of fine powder acetylene black was increased to 50% by weight and the battery of Example 5 in which the amount of fine powder acetylene black was increased to 100% by weight had a discharge duration of: Both the continuous discharge and the intermittent discharge were longer than the battery of Comparative Example 1, indicating that the discharge capacity at the time of heavy load discharge was large.

Examples 6 to 8 and Comparative Examples 7 to 8 The composition and amount of manganese dioxide were the same as in Example 1, and the ratio of zinc chloride in the electrolytic solution to this manganese dioxide (ZnCl ₂ / MnO ₂ ) was determined by weight. ZnCl ₂ / MnO ₂ = 0.180
(Comparative Example 7), ZnCl ₂ / MnO ₂ = 0.200 (Comparative Example 8), ZnCl ₂
SUM was carried out in the same manner as in Example 1 except that / MnO ₂ = 0.210 (Example 6), ZnCl ₂ / MnO ₂ = 0.230 (Example 7) and ZnCl ₂ / MnO ₂ = 0.273 (Example 8). A -1 type zinc chloride dry cell having the same structure as that shown in FIG. 1 was produced.

The batteries of Examples 6 to 8 and Comparative Examples 7 to 8 were subjected to intermittent discharge at a load of 2Ω according to JIS C 8501, and the discharge duration was measured. From the results, the discharge duration per manganese dioxide unit amount was determined. Was. The relationship between the ratio of zinc chloride in the electrolytic solution to manganese dioxide (ZnCl ₂ / MnO ₂ ) and the duration of discharge per unit amount of manganese dioxide is shown in FIG.
It is shown in the table. Table 6 also shows the results of the batteries of Example 1 and Comparative Example 1 in order to make it easier to understand the relationship between ZnCl ₂ / MnO ₂ and the discharge duration per unit amount of manganese dioxide. .

As shown in Table 6, the batteries of Examples 1 and 6-8 ratio of zinc chloride electrolyte for manganese dioxide (ZnCl _{2 2} / MnO ₂₎ is in the range of 0.210 to 0.273, dioxide The discharge duration time per unit amount of manganese was long, indicating that the discharge utilization amount of manganese dioxide was high. However, in the battery of Example 8 in which ZnCl ₂ / MnO ₂ = 0.273, a decrease in the discharge duration per unit amount of manganese dioxide began to be observed. This is because the discharge utilization rate of manganese dioxide itself seems to increase with an increase in ZnCl ₂ / MnO ₂ , but the decrease in the amount of water in the electrolytic solution makes it difficult for the discharge reaction to proceed. it is conceivable that.

〔The invention's effect〕

As described above, in the present invention, fine powdered manganese dioxide having 90% by weight or more in the range of particle diameter of 1 to 10 μm is used in 20 to 40% by weight of the total manganese dioxide, and the iodine adsorption amount is 25%.
A fine powdered acetylene black of 0 to 310 mg / g is used in an amount of 5% by weight or more of the total acetylene black, and the weight ratio of zinc chloride in the electrolyte to manganese dioxide (ZnCl ₂ / MnO ₂ ) is ZnCl ₂ / MnO _2. By using a zinc chloride electrolyte having a high concentration of 0.210 to 0.273, it was possible to provide a zinc chloride dry battery having a large discharge capacity and a small decrease in discharge performance during storage.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing an example of a zinc chloride type dry battery according to the present invention. (1) ... zinc can, (2) ... separator, (4) ... positive electrode mixture

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroshi Kakuno 1-88 Ushitora, Ibaraki-shi, Osaka Hitachi Maxell, Ltd. (56) References JP-A-60-9060 (JP, A) JP-A Sho 62-157676 (JP, A) JP-A-49-6416 (JP, A) JP-A-50-110034 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) H01M 6/06 H01M 4/50 H01M 4/62

Claims (1)

(57) [Claims] 1. A manganese dioxide containing 20 to 40% by weight of fine manganese dioxide having a particle diameter of 1 to 10 μm in a range of 90% by weight or more is used as a positive electrode active material, and a fine powder having an iodine adsorption amount of 250 to 310 mg / g is used. Acetylene black containing 5% by weight or more of powdered acetylene black is used as a conductive additive, and the amount ratio of zinc chloride in the electrolyte to manganese dioxide (Zn
A zinc chloride type dry battery characterized by using a zinc chloride type electrolyte in which Cl ₂ / MnO ₂ ) is ZnCl ₂ / MnO ₂ = 0.210 to 0.273 by weight ratio.