JPWO2007004632A1 - Stacked manganese battery - Google Patents

Abstract

The present invention reduces the environmental impact by reducing the amount of lead in the negative electrode zinc plate than before, improves the strength and corrosion resistance of the negative electrode zinc plate, and has high reliability with excellent high-rate discharge characteristics and storage characteristics. It is an object of the present invention to provide a multilayer manganese dry battery. The present invention includes a cup-shaped heat-shrinkable resin tube having a hole in the center of the bottom surface, and a unit cell case made of a negative electrode zinc plate disposed on the inside of the bottom surface of the heat-shrinkable resin tube and having a carbon film on one side; A plurality of unit cells each including a separator made of paper coated with a paste material and a positive electrode mixture housed in the unit cell case via the separator disposed inside the unit cell case; A multilayer manganese dry battery, wherein the negative electrode zinc plate has a Vickers hardness of 45 to 55 Hv.

Description

  The present invention relates to a laminated manganese dry battery, and more particularly to improvement of a negative electrode zinc plate.

  Conventionally, 0.4% by weight of lead has been added to the negative electrode zinc plate of the laminated manganese dry battery in order to improve the corrosion resistance of zinc. However, in recent years, in order to prevent environmental pollution caused by dry batteries after use, there has been a strong demand for using no harmful substances such as lead as much as possible for the constituent members of the batteries.

In a cylindrical manganese dry battery, as a method for improving the corrosion resistance of the negative electrode zinc can, for example, it is proposed to add an In chloride or a Bi compound to the paste applied to the separator paper (patent) References 1 and 2).
However, when In or Bi is added, there is a problem that high-rate discharge characteristics are deteriorated. In addition, in the laminated manganese dry battery, the strength of the zinc plate is insufficient, and thus there may be a case where the open circuit voltage is poor after the battery is assembled.

In addition, in a cylindrical manganese dry battery, it has been proposed to add In or the like to a lead-free negative electrode zinc can (Patent Document 3).
The negative electrode zinc can of a cylindrical manganese dry battery is designed in consideration of rolling processability in the can-making process and mechanical strength in the battery assembly process after the can-making process.

  On the other hand, the negative electrode of the laminated manganese dry battery is a zinc plate, and after stacking a plurality of unit cells including the zinc plate, the laminate is tightened from the stacking direction to assemble the battery. Force is applied in the direction. In a conventional zinc plate to which lead is added, the above-described force is applied to the unit cell during battery assembly, so that the zinc plate may bend and an open circuit voltage failure may occur.

Since the structure of the laminated manganese dry battery and the shape of the negative electrode are different from those of the cylindrical manganese dry battery, the negative electrode zinc plate of the laminated manganese dry battery needs to be independently examined. However, as for the negative electrode zinc plate of the laminated manganese dry battery, the mechanical strength, the corrosion resistance and the like have not been sufficiently studied yet.
JP-A-61-78051 JP-A-5-159767 JP-A-8-17424

  Therefore, in order to solve the above-described conventional problems, the present invention reduces the environmental load by reducing the amount of lead in the negative electrode zinc plate than before, improves the strength and corrosion resistance of the negative electrode zinc plate, and increases the rate. An object of the present invention is to provide a highly reliable laminated manganese dry battery excellent in discharge characteristics and storage characteristics.

The present invention includes a cup-shaped heat-shrinkable resin tube having a hole in the center of the bottom surface, and a unit cell case made of a negative electrode zinc plate disposed on the inside of the bottom surface of the heat-shrinkable resin tube and having a carbon film on one side; A plurality of unit cells each including a separator made of paper coated with a paste material and a positive electrode mixture housed in the unit cell case via the separator disposed inside the unit cell case; A laminated manganese dry battery, wherein the zinc plate surface has a Vickers hardness of 45 to 55 Hv.
Thereby, the open circuit voltage defect which generate | occur | produces at the time of battery manufacture can be reduced.

The zinc plate is preferably made of a zinc alloy containing 0.03 parts by weight or less of Pb and 0.001 to 0.01 parts by weight of In per 100 parts by weight of zinc.
The separator contains at least one chloride of In chloride and Bi chloride, and the total content of In and Bi in the chloride contained in the separator is the dry solid component 100 in the paste material. It is preferably 0.01 to 1.0 part by weight per part by weight.

  According to the present invention, since the strength of the negative electrode zinc plate is improved, it is possible to reduce open circuit voltage failure during battery production. In addition, the corrosion resistance of the negative electrode zinc plate is improved, and a laminated manganese dry battery excellent in high rate discharge characteristics and storage characteristics can be obtained. Since the amount of lead in the negative electrode zinc plate can be reduced, the environmental load is reduced.

It is a longitudinal cross-sectional view of the unit cell in the laminated manganese dry battery of this invention. It is a longitudinal cross-sectional view of the unit cell case in the multilayer manganese dry battery of this invention. It is the front view which made a section of a lamination type manganese dry battery of the present invention a section.

  As a result of various studies on the mechanical strength of the negative electrode zinc plate in the multilayer manganese dry battery, the present inventor has found that the zinc plate contains a zinc alloy containing 0.001 part by weight or more of In per 100 parts by weight of zinc. It has been found that the Vickers hardness is 45 Hv or more, deformation of the zinc plate due to the force applied from the up and down direction during battery production is suppressed, and the occurrence of open circuit voltage failure can be suppressed. On the other hand, if the In content exceeds 0.01 parts by weight and the Vickers hardness exceeds 55 Hv, cracks are likely to occur during the production of the zinc plate.

  Moreover, since the corrosion resistance of the zinc plate is improved at the same time as the above effects, the conventional lead is reduced to 0 even at 0.03 parts by weight or less per 100 parts by weight of zinc, which is a lead amount in which the corrosion resistance effect by lead is remarkably reduced. High rate discharge characteristics and storage characteristics equivalent to or higher than those obtained when a zinc plate containing 4 parts by weight is used.

  The Vickers hardness of said zinc plate is calculated | required by the Vickers hardness test method of JISZ2244 regulation, for example.

An embodiment of the multilayer manganese dry battery of the present invention will be described with reference to FIG. FIG. 3 is a front view showing a part of the laminated manganese dry battery of the present invention in cross section and showing the inside of the battery.
A battery group including a plurality of stacked unit cells 7 and a positive electrode current collector plate 5 in contact with the upper end surface thereof is covered with a heat-shrinkable resin tube 4 made of, for example, polyvinyl chloride from the side surface to the upper and lower end edges. The outer can 10 is housed. The heat-shrinkable resin tube 4 has its upper and lower edges closely adhered to the upper and lower edges of the battery group due to heat shrinkage.

  A positive electrode terminal 1 provided on the terminal plate 3 is connected to a positive electrode current collector plate 5 through a positive electrode lead 6. On the other hand, the negative electrode terminal 2 provided on the terminal plate 3 is connected to the lower end surface of the battery group via the negative electrode lead 8. The terminal plate 3 and the bottom plate 9 are tightened by bending the upper and lower ends of the outer can 10 inward.

Here, the longitudinal cross-sectional view of the unit cell in the laminated manganese dry battery of this invention is shown in FIG. Moreover, the longitudinal cross-sectional view of the unit cell case in the laminated manganese dry battery of this invention is shown in FIG.
The unit cell 7 includes a cup-shaped heat-shrinkable resin tube 12 made of, for example, polyvinyl chloride having a hole in the center of the bottom surface as shown in FIG. 2 and zinc disposed inside the bottom surface of the heat-shrinkable resin tube 12. -It consists of a unit cell case made of carbon-bonded electrode plate 16, a separator 13 disposed inside the unit cell case, and a positive electrode mixture 14 accommodated in the unit cell case via the separator 13.

The zinc-carbon bond electrode plate 16 includes a zinc plate 11 in contact with the separator 13 and a carbon film 15 formed on the lower surface thereof. Further, the heat-shrinkable resin tube 12 and the carbon film 15 are bonded by an adhesive 17 having a vinyl chloride-vinyl acetate copolymer as a main component.
The zinc plate contains 0.03 parts by weight or less of Pb and 0.001 to 0.01 parts by weight of In with respect to 100 parts by weight of zinc. Thereby, the corrosion resistance of the zinc plate is improved, and excellent high rate discharge characteristics and storage characteristics are obtained. Moreover, since the amount of lead can be reduced as compared with the conventional case, the environmental load can be reduced.

  When the plurality of unit cells 7 are stacked in the vertical direction, the carbon film 15 of the zinc-carbon bond electrode plate 16 exposed from the hole at the center of the bottom surface of the heat-shrinkable resin tube 12 of the unit cell 7 positioned above, and below These unit cells are connected in series by contacting a portion of the positive electrode mixture 14 of the unit cell 7 that is not covered with the heat-shrinkable resin tube 12.

  In the laminated manganese dry battery as described above, when the outer can 10 is bent in the final process of battery assembly, force is applied in the vertical direction (stacking direction) of the group of stacked unit cells 7, but the zinc plate has an In value of 0.1. By including 001 to 0.01 parts by weight, since the Vickers hardness of the zinc plate is 45 Hv or more, deformation such as deflection can be greatly reduced, and the occurrence of open circuit voltage failure after battery assembly can be suppressed.

The separator 13 is made of a paste material applied to a contact surface (outer bottom surface) of the cup-shaped paper and the zinc plate 11 of the paper. As the separator 13, for example, a kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried is used.
The separator 13 contains at least one chloride of In chloride (InCl ₃ ) and Bi chloride (BiCl ₃ ), and the total content of In and Bi in the chloride contained in the separator 13 is a paste. The amount is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the dry solid component in the material. In this case, the corrosion resistance of the zinc plate is improved and the storage characteristics are improved.

  When the total content of In and Bi in the separator 13 is less than 0.01 parts by weight per 100 parts by weight of the dry solid component in the paste material, the effect of In or Bi becomes insufficient. On the other hand, when the total content of In and Bi in the separator 13 exceeds 1.0 part by weight per 100 parts by weight of the dry solid component in the paste material, the high rate discharge performance is deteriorated.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
<< Examples 1-4 and Comparative Examples 1-6 >>
The unit cell shown in FIG. 1 was produced as follows.
A vinyl chloride-vinyl acetate copolymer comprising a carbon film 15 formed on one side of a zinc plate 11 in a zinc-carbon bond electrode plate 16 and an inner bottom surface of a cup-shaped heat-shrinkable resin tube 12 made of polyvinyl chloride. Was bonded with an adhesive 17 containing as a main component, to obtain a unit cell case shown in FIG. 2 composed of a zinc-carbon bond electrode plate 16 and a heat-shrinkable resin tube 12.

  After the cup-shaped separator 13 was disposed in the unit cell case, an electrolytic solution was injected into the separator 13. The separator 13 was a kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried. As the electrolytic solution, an aqueous solution containing 30% by weight of zinc chloride and 1% by weight of ammonium chloride was used. And after inserting the positive mix 14 inside the separator 13, the resin tube 12 was heat-shrinked and the unit cell 7 was produced. As the positive electrode mixture 14, manganese dioxide, acetylene black, and the same electrolytic solution as described above were kneaded at a weight ratio of 4.5: 1: 2.5 and formed into a pellet shape.

Next, the manganese dry battery shown in FIG. 3 was assembled as follows.
Six unit cells 7 were stacked with the positive electrode mixture facing upward, and the positive electrode current collector plate 5 was further arranged on the upper surface of the uppermost unit cell 7 to constitute a battery group. The battery group was covered with a heat-shrinkable resin tube 4 made of polyvinyl chloride, and the heat-shrinkable resin tube 4 was heat-shrinked so that the upper and lower ends thereof were brought into close contact with the upper and lower ends of the battery group.

  This battery group was inserted into the outer can 10 together with an assembled terminal board in which the terminal board 3 and the bottom board 9 were combined. The upper and lower edges of the outer can 10 were bent to tighten the terminal plate 3 and the bottom plate 9. The positive electrode lead 6 connected to the positive electrode terminal 1 provided on the terminal plate 3 was brought into contact with the positive electrode current collector plate 5. Moreover, the negative electrode lead 8 connected from the negative electrode of the lowermost unit cell 7 to the upper surface of the positive electrode current collector plate 5 along the side surface of the battery group was brought into contact with the negative electrode terminal 2 provided on the terminal plate 3.

In the production of the above-mentioned laminated manganese dry battery, a zinc metal having a purity of 99.99% by weight was dissolved so that the zinc plate contained Pb and In in amounts shown in Table 1 per 100 parts by weight of zinc. A certain amount of Pb and In were added to obtain a zinc alloy. Using this zinc alloy, a zinc plate having a thickness of 0.34 mm was produced by cold rolling.
Moreover, the zinc plate was produced similarly to the above also about the case where only Pb is included as a comparison (Comparative Examples 1 to 3) and the case where Pb and In are not included (Comparative Example 4).

[Evaluation]
(1) Measurement of mechanical strength of zinc plate About the zinc plate obtained above, the Vickers hardness was measured based on the Vickers hardness test method of JIS Z2244.
(2) Incidence rate of open circuit voltage failure during battery fabrication Each battery was fabricated in 1000 pieces, and the percentage of batteries that had open circuit voltage failure was examined. At this time, in the open circuit voltage distribution of each battery, it was determined that an open circuit voltage failure occurred for the battery whose open circuit voltage was −50 mV or less from the mode value.

(3) Evaluation of high rate discharge characteristics of batteries immediately after production (first time) Each battery immediately after production was discharged with a load of 180Ω (end voltage: 5.4 V), and the discharge time at this time was measured.
(4) Evaluation of storage characteristics of batteries Each battery immediately after production was stored in a 45 ° C environment for 3 months. And each battery after a preservation | save was discharged on the conditions similar to said (3), and the discharge time at this time was investigated.
The evaluation results are shown in Table 2.

  From Comparative Examples 1 to 4, as the Pb content in the zinc plate was smaller, the corrosion resistance of the zinc plate was lowered and the storage characteristics were deteriorated. Moreover, since Vickers hardness was less than 45 Hv, the battery which generate | occur | produced the open circuit voltage defect at the time of battery preparation was seen.

  On the other hand, when the In content was 0.001 to 0.01 parts by weight per 100 parts by weight of zinc, the corrosion resistance of the zinc plate was improved, and the storage characteristics were improved. In addition, since the Vickers hardness was 45 Hv or more and the zinc plate was not deformed during battery production, no open circuit voltage failure was observed. In Comparative Example 5 in which the In content was 0.0005 parts by weight per 100 parts by weight of zinc, a battery having a Vickers hardness of less than 45 Hv and causing an open circuit voltage failure when the battery was produced was seen. On the other hand, in Comparative Example 6 in which the In content was 0.02 parts by weight per 100 parts by weight of zinc, cracks occurred in the zinc plate during the production of the zinc plate, and it could not be used as the negative electrode.

<< Examples 5 to 18 >>
InCl ₃ or BiCl ₃ was added to the separator paste so that the separator contained the amount of In or Bi shown in Table 3 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 4.

  When the content of In or Bi was 0.01 to 1 part by weight per 100 parts by weight of the dry solid component of the paste material, the storage characteristics of the battery were improved.

<< Examples 19 to 30 >>
InCl ₃ and BiCl ₃ were added to the separator paste so that the separator contained In and Bi at a rate shown in Table 5 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 6.

  When the total content of In and Bi was 0.01 to 1% by weight per 100 parts by weight of the dry solid component of the paste material, the storage characteristics were further improved.

<< Examples 31-36 >>
A negative electrode zinc plate was produced in the same manner as in Example 1 except that lead was not added and 0.0025 part by weight of In was added per 100 parts by weight of zinc. Then, InCl ₃ or BiCl ₃ was added to the separator paste so that the separator contained the amount of In or Bi shown in Table 7 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 8.

  Even when lead is not added, by adding In to the zinc plate and including In or Bi in the separator, the occurrence of open circuit voltage failure during battery fabrication is suppressed, and excellent high-rate discharge characteristics and storage characteristics was gotten.

  The multilayer manganese dry battery of the present invention has excellent high rate discharge characteristics and storage characteristics, and is suitably used as a power source for electronic equipment such as information equipment and portable equipment.

  The present invention relates to a laminated manganese dry battery, and more particularly to improvement of a negative electrode zinc plate.

  Conventionally, 0.4% by weight of lead has been added to the negative electrode zinc plate of the laminated manganese dry battery in order to improve the corrosion resistance of zinc. However, in recent years, in order to prevent environmental pollution caused by dry batteries after use, there has been a strong demand for using no harmful substances such as lead as much as possible for the constituent members of the batteries.

In a cylindrical manganese dry battery, as a method for improving the corrosion resistance of the negative electrode zinc can, for example, it is proposed to add an In chloride or a Bi compound to the paste applied to the separator paper (patent) References 1 and 2).
However, when In or Bi is added, there is a problem that high-rate discharge characteristics are deteriorated. In addition, in the laminated manganese dry battery, the strength of the zinc plate is insufficient, and thus there may be a case where the open circuit voltage is poor after the battery is assembled.

In addition, in a cylindrical manganese dry battery, it has been proposed to add In or the like to a lead-free negative electrode zinc can (Patent Document 3).
The negative electrode zinc can of a cylindrical manganese dry battery is designed in consideration of rolling processability in the can-making process and mechanical strength in the battery assembly process after the can-making process.

  On the other hand, the negative electrode of the laminated manganese dry battery is a zinc plate, and after stacking a plurality of unit cells including the zinc plate, the laminate is tightened from the stacking direction to assemble the battery. Force is applied in the direction. In a conventional zinc plate to which lead is added, the above-described force is applied to the unit cell during battery assembly, so that the zinc plate may bend and an open circuit voltage failure may occur.

Since the structure of the laminated manganese dry battery and the shape of the negative electrode are different from those of the cylindrical manganese dry battery, the negative electrode zinc plate of the laminated manganese dry battery needs to be independently examined. However, as for the negative electrode zinc plate of the laminated manganese dry battery, the mechanical strength, the corrosion resistance and the like have not been sufficiently studied yet.
JP-A-61-78051 JP-A-5-159767 JP-A-8-17424

  Therefore, in order to solve the above-described conventional problems, the present invention reduces the environmental load by reducing the amount of lead in the negative electrode zinc plate than before, improves the strength and corrosion resistance of the negative electrode zinc plate, and increases the rate. An object of the present invention is to provide a highly reliable laminated manganese dry battery excellent in discharge characteristics and storage characteristics.

The present invention includes a cup-shaped heat-shrinkable resin tube having a hole in the center of the bottom surface, and a unit cell case made of a negative electrode zinc plate disposed on the inside of the bottom surface of the heat-shrinkable resin tube and having a carbon film on one side; A plurality of unit cells each including a separator made of paper coated with a paste material and a positive electrode mixture housed in the unit cell case via the separator disposed inside the unit cell case; A laminated manganese dry battery, wherein the zinc plate surface has a Vickers hardness of 45 to 55 Hv.
Thereby, the open circuit voltage defect which generate | occur | produces at the time of battery manufacture can be reduced.

The zinc plate is preferably made of a zinc alloy containing 0.03 parts by weight or less of Pb and 0.001 to 0.01 parts by weight of In per 100 parts by weight of zinc.
The separator contains at least one of In chloride and Bi chloride;
The total content of In and Bi in the chloride contained in the separator is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the dry solid component in the paste material.

  According to the present invention, since the strength of the negative electrode zinc plate is improved, it is possible to reduce open circuit voltage failure during battery production. In addition, the corrosion resistance of the negative electrode zinc plate is improved, and a laminated manganese dry battery excellent in high rate discharge characteristics and storage characteristics can be obtained. Since the amount of lead in the negative electrode zinc plate can be reduced, the environmental load is reduced.

  As a result of various studies on the mechanical strength of the negative electrode zinc plate in the multilayer manganese dry battery, the present inventor found that the zinc plate contained a zinc alloy containing 0.001 part by weight or more of In per 100 parts by weight of zinc. It has been found that the Vickers hardness is 45 Hv or more, deformation of the zinc plate due to the force applied from the up and down direction during battery production is suppressed, and the occurrence of open circuit voltage failure can be suppressed. On the other hand, if the In content exceeds 0.01 parts by weight and the Vickers hardness exceeds 55 Hv, cracks are likely to occur during the production of the zinc plate.

  Moreover, since the corrosion resistance of the zinc plate is improved at the same time as the above effects, the conventional lead is reduced to 0 even at 0.03 parts by weight or less per 100 parts by weight of zinc, which is a lead amount in which the corrosion resistance effect by lead is remarkably reduced. High rate discharge characteristics and storage characteristics equivalent to or higher than those obtained when a zinc plate containing 4 parts by weight is used.

  The Vickers hardness of the zinc plate is determined by, for example, the Vickers hardness test method specified in JIS Z 2244.

An embodiment of the multilayer manganese dry battery of the present invention will be described with reference to FIG. FIG. 3 is a front view showing a part of the laminated manganese dry battery of the present invention in cross section and showing the inside of the battery.
A battery group including a plurality of stacked unit cells 7 and a positive electrode current collector plate 5 in contact with the upper end surface thereof is covered with a heat-shrinkable resin tube 4 made of, for example, polyvinyl chloride from the side surface to the upper and lower end edges. The outer can 10 is housed. The heat-shrinkable resin tube 4 has its upper and lower edges closely adhered to the upper and lower edges of the battery group due to heat shrinkage.

  A positive electrode terminal 1 provided on the terminal plate 3 is connected to a positive electrode current collector plate 5 through a positive electrode lead 6. On the other hand, the negative electrode terminal 2 provided on the terminal plate 3 is connected to the lower end surface of the battery group via the negative electrode lead 8. The terminal plate 3 and the bottom plate 9 are tightened by bending the upper and lower ends of the outer can 10 inward.

Here, the longitudinal cross-sectional view of the unit cell in the laminated manganese dry battery of this invention is shown in FIG. Moreover, the longitudinal cross-sectional view of the unit cell case in the laminated manganese dry battery of this invention is shown in FIG.
The unit cell 7 includes a cup-shaped heat-shrinkable resin tube 12 made of, for example, polyvinyl chloride having a hole in the center of the bottom surface as shown in FIG. 2 and zinc disposed inside the bottom surface of the heat-shrinkable resin tube 12. -It consists of a unit cell case made of carbon-bonded electrode plate 16, a separator 13 disposed inside the unit cell case, and a positive electrode mixture 14 accommodated in the unit cell case via the separator 13.

The zinc-carbon bond electrode plate 16 includes a zinc plate 11 in contact with the separator 13 and a carbon film 15 formed on the lower surface thereof. Further, the heat-shrinkable resin tube 12 and the carbon film 15 are bonded by an adhesive 17 having a vinyl chloride-vinyl acetate copolymer as a main component.
The zinc plate contains 0.03 parts by weight or less of Pb and 0.001 to 0.01 parts by weight of In with respect to 100 parts by weight of zinc. Thereby, the corrosion resistance of the zinc plate is improved, and excellent high rate discharge characteristics and storage characteristics are obtained. Moreover, since the amount of lead can be reduced as compared with the conventional case, the environmental load can be reduced.

  When the plurality of unit cells 7 are stacked in the vertical direction, the carbon film 15 of the zinc-carbon bond electrode plate 16 exposed from the hole at the center of the bottom surface of the heat-shrinkable resin tube 12 of the unit cell 7 positioned above, and below These unit cells are connected in series by contacting a portion of the positive electrode mixture 14 of the unit cell 7 that is not covered with the heat-shrinkable resin tube 12.

  In the laminated manganese dry battery as described above, when the outer can 10 is bent in the final process of battery assembly, force is applied in the vertical direction (stacking direction) of the group of stacked unit cells 7, but the zinc plate has an In value of 0.1. By including 001 to 0.01 parts by weight, since the Vickers hardness of the zinc plate is 45 Hv or more, deformation such as deflection can be greatly reduced, and the occurrence of open circuit voltage failure can be suppressed after battery assembly.

The separator 13 is made of a paste material applied to a contact surface (outer bottom surface) of the cup-shaped paper and the zinc plate 11 of the paper. As the separator 13, for example, a kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried is used.
The separator 13 contains at least one chloride of In chloride (InCl ₃ ) and Bi chloride (BiCl ₃ ), and the total content of In and Bi in the chloride contained in the separator 13 is a paste. The amount is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the dry solid component in the material. In this case, the corrosion resistance of the zinc plate is improved and the storage characteristics are improved.

  When the total content of In and Bi in the separator 13 is less than 0.01 parts by weight per 100 parts by weight of the dry solid component in the paste material, the effect of In or Bi becomes insufficient. On the other hand, when the total content of In and Bi in the separator 13 exceeds 1.0 part by weight per 100 parts by weight of the dry solid component in the paste material, the high rate discharge performance is deteriorated.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
<< Examples 1-4 and Comparative Examples 1-6 >>
The unit cell shown in FIG. 1 was produced as follows.
A vinyl chloride-vinyl acetate copolymer comprising a carbon film 15 formed on one side of a zinc plate 11 in a zinc-carbon bond electrode plate 16 and an inner bottom surface of a cup-shaped heat-shrinkable resin tube 12 made of polyvinyl chloride. Was bonded with an adhesive 17 containing as a main component, to obtain a unit cell case shown in FIG. 2 composed of a zinc-carbon bond electrode plate 16 and a heat-shrinkable resin tube 12.

  After the cup-shaped separator 13 was disposed in the unit cell case, an electrolytic solution was injected into the separator 13. The separator 13 was a kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of vinyl acetate in an alcohol solvent and dried. As the electrolytic solution, an aqueous solution containing 30% by weight of zinc chloride and 1% by weight of ammonium chloride was used. And after inserting the positive mix 14 inside the separator 13, the resin tube 12 was heat-shrinked and the unit cell 7 was produced. As the positive electrode mixture 14, manganese dioxide, acetylene black, and the same electrolytic solution as described above were kneaded at a weight ratio of 4.5: 1: 2.5 and formed into a pellet shape.

Next, the manganese dry battery shown in FIG. 3 was assembled as follows.
Six unit cells 7 were stacked with the positive electrode mixture facing upward, and the positive electrode current collector plate 5 was further arranged on the upper surface of the uppermost unit cell 7 to constitute a battery group. The battery group was covered with a heat-shrinkable resin tube 4 made of polyvinyl chloride, and the heat-shrinkable resin tube 4 was heat-shrinked so that the upper and lower ends thereof were brought into close contact with the upper and lower ends of the battery group.

  This battery group was inserted into the outer can 10 together with an assembled terminal board in which the terminal board 3 and the bottom board 9 were combined. The upper and lower edges of the outer can 10 were bent to tighten the terminal plate 3 and the bottom plate 9. The positive electrode lead 6 connected to the positive electrode terminal 1 provided on the terminal plate 3 was brought into contact with the positive electrode current collector plate 5. Moreover, the negative electrode lead 8 connected from the negative electrode of the lowermost unit cell 7 to the upper surface of the positive electrode current collector plate 5 along the side surface of the battery group was brought into contact with the negative electrode terminal 2 provided on the terminal plate 3.

In the production of the above-mentioned laminated manganese dry battery, a zinc metal having a purity of 99.99% by weight was dissolved so that the zinc plate contained Pb and In in amounts shown in Table 1 per 100 parts by weight of zinc. A certain amount of Pb and In were added to obtain a zinc alloy. Using this zinc alloy, a zinc plate having a thickness of 0.34 mm was produced by cold rolling.
Moreover, the zinc plate was produced similarly to the above also about the case where only Pb is included as a comparison (Comparative Examples 1 to 3) and the case where Pb and In are not included (Comparative Example 4).

[Evaluation]
(1) Measurement of mechanical strength of zinc plate Vickers hardness of the zinc plate obtained above was measured based on the Vickers hardness test method of JIS Z 2244.
(2) Incidence rate of open circuit voltage failure during battery fabrication Each battery was fabricated in 1000 pieces, and the percentage of batteries that had open circuit voltage failure was examined. At this time, in the open circuit voltage distribution of each battery, it was determined that an open circuit voltage failure occurred for the battery whose open circuit voltage was −50 mV or less from the mode value.

(3) Evaluation of high rate discharge characteristics of batteries immediately after production (first time) Each battery immediately after production was discharged with a load of 180Ω (end voltage: 5.4 V), and the discharge time at this time was measured.
(4) Evaluation of storage characteristics of batteries Each battery immediately after production was stored in a 45 ° C environment for 3 months. And each battery after a preservation | save was discharged on the conditions similar to said (3), and the discharge time at this time was investigated.
The evaluation results are shown in Table 2.

  From Comparative Examples 1 to 4, as the Pb content in the zinc plate was smaller, the corrosion resistance of the zinc plate was lowered and the storage characteristics were deteriorated. Moreover, since Vickers hardness was less than 45 Hv, the battery which generate | occur | produced the open circuit voltage defect at the time of battery preparation was seen.

  On the other hand, when the In content was 0.001 to 0.01 parts by weight per 100 parts by weight of zinc, the corrosion resistance of the zinc plate was improved, and the storage characteristics were improved. In addition, since the Vickers hardness was 45 Hv or more and the zinc plate was not deformed during battery production, no open circuit voltage failure was observed. In Comparative Example 5 in which the In content was 0.0005 parts by weight per 100 parts by weight of zinc, a battery having a Vickers hardness of less than 45 Hv and causing an open circuit voltage failure when the battery was produced was seen. On the other hand, in Comparative Example 6 in which the In content was 0.02 parts by weight per 100 parts by weight of zinc, cracks occurred in the zinc plate during the production of the zinc plate, and it could not be used as the negative electrode.

<< Examples 5 to 18 >>
InCl ₃ or BiCl ₃ was added to the separator paste so that the separator contained the amount of In or Bi shown in Table 3 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 4.

  When the content of In or Bi was 0.01 to 1 part by weight per 100 parts by weight of the dry solid component of the paste material, the storage characteristics of the battery were improved.

<< Examples 19 to 30 >>
InCl ₃ and BiCl ₃ were added to the separator paste so that the separator contained In and Bi at a rate shown in Table 5 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 6.

  When the total content of In and Bi was 0.01 to 1% by weight per 100 parts by weight of the dry solid component of the paste material, the storage characteristics were further improved.

<< Examples 31-36 >>
A negative electrode zinc plate was produced in the same manner as in Example 1 except that lead was not added and 0.0025 part by weight of In was added per 100 parts by weight of zinc. Then, InCl ₃ or BiCl ₃ was added to the separator paste so that the separator contained the amount of In or Bi shown in Table 7 per 100 parts by weight of the dry solid component of the paste. Except for this, a stacked manganese dry battery was produced in the same manner as in Example 2 and evaluated in the same manner as described above. These evaluation results are shown in Table 8.

  Even when lead is not added, by adding In to the zinc plate and including In or Bi in the separator, the occurrence of open circuit voltage failure during battery fabrication is suppressed, and excellent high rate discharge characteristics and storage characteristics was gotten.

  The multilayer manganese dry battery of the present invention has excellent high rate discharge characteristics and storage characteristics, and is suitably used as a power source for electronic equipment such as information equipment and portable equipment.

It is a longitudinal cross-sectional view of the unit cell in the laminated manganese dry battery of this invention. It is a longitudinal cross-sectional view of the unit cell case in the multilayer manganese dry battery of this invention. It is the front view which made a section of a lamination type manganese dry battery of the present invention a section.

Claims (3)

A cup-shaped heat-shrinkable resin tube having a hole in the center of the bottom surface, and a unit cell case made of a negative electrode zinc plate disposed on the bottom surface inside the heat-shrinkable resin tube and having a carbon film on one side;
A separator made of paper coated with a paste material disposed inside the unit cell case;
A laminated manganese dry battery including a plurality of unit cells, and a positive electrode mixture housed in the unit cell case via the separator,
The laminated manganese dry battery, wherein the zinc plate has a Vickers hardness of 45 to 55 Hv.   The multilayer manganese dry battery according to claim 1, wherein the zinc plate is made of a zinc alloy containing 0.03 parts by weight or less of Pb and 0.001 to 0.01 parts by weight of In per 100 parts by weight of zinc. The separator contains at least one of In chloride and Bi chloride;
The laminated form according to claim 1, wherein the total content of In and Bi in the chloride contained in the separator is 0.01 to 1.0 part by weight per 100 parts by weight of the dry solid component in the paste material. Manganese dry battery.

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