JP2005129297A - Manganese dry cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manganese dry cell of small inner resistance, of superior electric discharge property, and of a superior storage property by preserving corrosion resistance of an indium film formed on the surface of a cathode can made of zinc over a long period of time from the initial period. <P>SOLUTION: The manganese dry cell is provided with an anode mixture having manganese dioxide as an active material, the cathode can made of zinc, and a separator consisting of a paper applied with a paste material. The separator contains indium chloride and indium oxide as the total indium conversion value of 0.01 to 3.0 pts. wt. against 100 pts. wt. of a dried solid component of the paste material, of which the weight ratio of the indium chloride and indium oxide in the indium conversion value is 30 to 70:70 to 30. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a manganese dry battery, and more particularly to an improvement in discharge performance.

Conventionally, as a method for suppressing an increase in internal resistance of a battery due to corrosion of a negative electrode can made of zinc, a method of forming an indium coating on the surface of the negative electrode can has been studied.
For example, Patent Document 1 proposes to add indium chloride or indium oxide to both the base material and the paste material of the separator.

Patent Document 2 proposes adding diindium trioxide to the positive electrode mixture or separator paste material.
These indium compounds are eluted in the electrolytic solution and deposited as metallic indium on the surface of the negative electrode can to form an indium film.

Indium chloride elutes early in the electrolyte, and indium is deposited on the negative electrode can made of zinc. For this reason, an increase in internal resistance due to corrosion of the negative electrode can can be suppressed in the initial stage of the battery. However, there is a problem that the effect of such indium is limited to an initial short period.
Further, indium oxide is gradually eluted into the electrolyte solution, so that an effect of suppressing an increase in internal resistance can be exhibited in a battery after long-term storage. However, the effect of such indium was insufficient in the initial and intermediate periods.
Japanese Patent Laid-Open No. 6-20672 JP-A-5-159775

  Therefore, in order to solve the above-described conventional problems, the present invention maintains the effect of improving the corrosion resistance of the negative electrode can by the indium coating formed on the surface of the negative electrode can made of zinc from the initial stage for an excellent discharge. An object of the present invention is to provide a manganese dry battery having characteristics and storage characteristics.

  The manganese dry battery of the present invention is a manganese dry battery comprising a positive electrode mixture containing manganese dioxide as an active material, a negative electrode can made of zinc, and a separator made of paper coated with a paste material, wherein the separator is a chloride of indium. And indium oxide in a total amount of 0.01 to 3.0 parts by weight in terms of indium relative to 100 parts by weight of the dry solid component in the paste material, and the indium chloride and indium oxide The weight ratio is 30 to 70:70 to 30 in terms of indium.

  According to the present invention, a manganese dry battery having excellent discharge characteristics and storage characteristics is provided by maintaining the effect of improving the corrosion resistance of the negative electrode can by the indium coating formed on the surface of the negative electrode can made of zinc for a long period from the beginning. can do.

  The present invention relates to a manganese dry battery comprising a positive electrode mixture containing manganese dioxide as an active material, a negative electrode can made of zinc, and a separator made of paper coated with a paste material, the separator comprising indium chloride and indium The total amount of the oxide is 0.01 to 3.0 parts by weight in terms of indium relative to 100 parts by weight of the dry solid component in the paste material, and the weight ratio of the indium chloride to the indium oxide is It is related with the manganese dry battery which is 30-70: 70-30 in an indium conversion value.

  That is, an amount of indium corresponding to 0.01 to 3.0% by weight of the dry solid component in the paste material is contained in the separator as indium chloride and indium oxide, and in the chloride as indium chloride. The weight ratio of indium contained to indium contained in the separator as an oxide of indium is 30 to 70:70 to 30.

Indium chloride and indium oxide contained in the separator are eluted into the electrolyte, and metal indium is deposited on the surface of the negative electrode can made of zinc to form an indium coating. Thereby, the corrosion resistance of the negative electrode can is improved.
Such an effect of indium becomes insufficient when the indium content is less than 0.01 parts by weight with respect to 100 parts by weight of the dry solid component in the paste material. On the other hand, when the content of indium exceeds 3.0 parts by weight with respect to 100 parts by weight of the dry solid component in the paste material, the amount of indium on the surface of the negative electrode can excessively increases, the internal resistance increases, and the discharge characteristics deteriorate. .

  Since the chloride of indium has a property of eluting into the electrolyte immediately after assembling the battery, the effect of indium is exhibited in the initial stage. Indium oxide has the property of gradually eluting into the electrolytic solution, so that the effect of indium is exhibited after the battery is left to some extent.

  When the weight ratio of the indium chloride to the indium oxide is 30 to 70:70 to 30 in terms of indium, both of the effects described above are exhibited, and the effect of indium lasts for a long period from the beginning. In addition, the negative electrode can can maintain excellent corrosion resistance against the electrolytic solution. For this reason, a manganese dry battery having low internal resistance, excellent discharge characteristics, and excellent storage characteristics can be obtained.

Examples of the indium chloride include indium trichloride (InCl ₃ ). Similar effects can be obtained with other halides, and examples include indium tribromide (InBr ₃ ), indium trifluoride (InF ₃ ), and indium triiodide (InI ₃ ).
Examples of the indium oxide include diindium trioxide (In ₂ O ₃ ) and diindium oxide (In ₂ O).

As the separator, for example, a kraft paper coated with a paste obtained by dissolving a crosslinked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried is used.
What is necessary is just to use what is used conventionally about the said positive mix and a negative electrode can.
Hereinafter, embodiments of the present invention will be described in detail.

An AA manganese dry battery was prepared according to the following procedure. FIG. 1 is a front view showing a cross section of a part of the AA manganese dry battery of the present invention.
A zinc alloy containing 0.4% by weight of lead was molded into a bottomed cylindrical shape, and a negative electrode can 4 was obtained. In this negative electrode can 4, the positive electrode mixture 1 was stored via a separator 3. At this time, in the positive electrode mixture, manganese dioxide as an active material, acetylene black as a conductive material, and an electrolyte solution containing 30% by weight of zinc chloride and 70% by weight of water were mixed at a weight ratio of 50:10:40. Things were used. The separator 3 was made of kraft paper coated with a paste obtained by dissolving a crosslinked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried. And the separator 3 was distribute | arranged so that the surface with which the paste material was apply | coated may oppose the negative electrode can 4, and the positive mix 1 and the negative electrode can 4 were isolated. A carbon rod 2 obtained by sintering carbon powder was inserted into the central portion of the positive electrode mixture 1.

A hole for inserting the carbon rod 2 was provided in the center of the sealing body 5 made of polyolefin resin. A paperboard 9 was obtained by punching the paperboard into a ring shape having a hole in the center. The carbon rods 2 were inserted into the holes of the sealing body 5 and the paper 9, respectively, and these were arranged on the upper part of the positive electrode mixture 1. And the upper part of the carbon rod 2 was made to contact the positive electrode terminal 11 so that it might act as a collector of a positive electrode.
A resin tube 8 made of a heat-shrinkable resin film is provided on the outer periphery of the negative electrode can 4 to cover the upper surface of the outer periphery of the sealing body 5 at its upper end and to be sealed at its lower end. The lower surface of the ring 7 was covered.

The positive electrode terminal 11 made of a tin plate was provided with a shape having a cap-shaped central portion and a flat plate-shaped flange portion that covers the upper end portion of the carbon rod 2. An insulating ring 12 made of resin was disposed on the flat collar portion of the positive electrode terminal 11. A bottom paper 13 was provided between the bottom of the positive electrode mixture 1 and the negative electrode can 4 in order to ensure insulation. A seal ring 7 is disposed on the outer surface side of the flat plate-like outer peripheral portion of the negative electrode terminal 6.
A metal outer can 10 made of a cylindrical tin plate is placed outside the resin tube 8, its lower end is bent inward, its upper end is curled inward, and its tip is insulated. It crimped to the ring 12.

  In the above manganese dry battery, in the separator paste material, indium trichloride and diindium trioxide are contained at a ratio shown in Table 1 in terms of indium with respect to 100 parts by weight of the dry solid component in the paste material. 1 was produced. The content in Table 1 indicates the amount of indium contained in the separator as indium trichloride and the amount of indium contained in the separator as diindium trioxide. For example, as shown in Table 1, in the case of a battery f containing 0.5 parts by weight of indium trichloride and diindium trioxide in terms of indium, the content of indium trichloride is 0.96 parts by weight. The content of diindium oxide is 0.60 parts by weight.

For comparison, as shown in Table 1, when not containing indium trichloride and diindium trioxide, when containing only 1.0 part by weight of indium trichloride in terms of indium, and only diindium trioxide. Batteries ac were also produced for each case containing 1.0 part by weight in terms of indium.
The batteries e to g, j and k are examples, and the batteries a to d, h, i and l are comparative examples.

[Evaluation]
The batteries a to l were evaluated as follows.
40 manganese dry batteries were produced, and the voltage of each battery immediately after production was measured. After storage at 45 ° C. for 10 days, the voltage of each battery was measured again. And the average value of the difference (voltage drop) of the voltage immediately after preparation and the voltage after 45 degreeC preservation | save was calculated | required.
The battery after storage at 45 ° C. for 10 days was subjected to a pulse discharge test in which discharge for 15 seconds under a load of 1.8Ω and discharge pause for 45 seconds were alternately repeated until the voltage reached 0.9V.

Also, when stored at 45 ° C. for 3 months, the average value of the voltage drop was determined in the same manner as described above, and a pulse discharge test was conducted.
The evaluation results are shown in Table 2. The discharge performance in the table represents the number of cycles when the discharge and the discharge pause are alternately repeated during the pulse discharge.

  Since battery a did not contain indium, the voltage drop was large, the discharge characteristics were lowered, and the storage characteristics were poor both after storage for 10 days and after storage for 3 months. Since battery b does not contain diindium trioxide, the voltage drop was large and the discharge characteristics were remarkably deteriorated after long-term storage for 3 months. Further, since the battery c does not contain indium trichloride, the voltage drop is large at the initial stage after storage for 10 days, the discharge characteristics are lowered, and good discharge characteristics are not obtained even after long-term storage.

  The batteries d to h using separators with various contents were compared with the weight ratio of indium trichloride and diindium trioxide being 1: 1 in terms of indium. As a result, a battery using a separator containing indium trichloride and diindium trioxide in a range of 0.01 to 3.0 parts by weight in terms of indium with respect to 100 parts by weight of the dry solid component in the paste material e to In g, it was found that both after storage for 10 days and after storage for 3 months, the voltage drop was small, good discharge characteristics were obtained, and excellent storage characteristics were obtained.

  However, since the content of indium trichloride and diindium trioxide in the battery d is as small as 0.006 parts by weight in terms of indium with respect to 100 parts by weight of the dry solid component in the paste material, the effect of indium is insufficient. Met. In battery h, although the voltage drop was small, the amount of indium present on the surface of the negative electrode can was too much, so the internal resistance increased and the discharge characteristics deteriorated.

  Further, the total content of indium trichloride and diindium trioxide is 1.0 part by weight in terms of indium with respect to 100 parts by weight of the dry solid component in the paste, and indium trichloride and diindium trioxide Batteries i to l using separators with various weight ratios were compared. As a result, in batteries j and k using a separator containing indium trichloride and diindium trioxide in a weight ratio of 30 to 70:70 to 30 in terms of indium, the batteries were stored for 10 days and for 3 months. In either case, it was found that the voltage drop was small, good discharge characteristics were obtained, and excellent storage characteristics were obtained. However, in batteries i and l, the voltage drop was large after storage for 3 months, and the discharge characteristics deteriorated.

  As described above, since the negative electrode can in the manganese dry battery of the present invention can maintain the effect of suppressing corrosion by indium for a long period from the beginning, it can be applied to a manganese dry battery that requires excellent discharge characteristics and storage characteristics.

It is the front view which made a part of manganese dry battery in the example of the present invention a section.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Positive electrode mixture 2 Carbon rod 3 Separator 4 Negative electrode can 5 Sealing body 6 Negative electrode terminal 7 Seal ring 8 Resin tube 9 Paper 10 Metal exterior can 11 Positive electrode terminal 12 Insulation ring 13 Bottom paper

Claims (1)

A manganese dry battery comprising a positive electrode mixture containing manganese dioxide as an active material, a negative electrode can made of zinc, and a separator made of paper coated with a paste material,
The separator contains indium chloride and indium oxide in a total amount of 0.01 to 3.0 parts by weight in terms of indium with respect to 100 parts by weight of the dry solid component in the paste material, and the indium chloride A manganese dry battery characterized in that the weight ratio of the oxide to the oxide of indium is 30 to 70:70 to 30 in terms of indium.

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