WO2008068929A1 - Élément de pile sèche au manganèse - Google Patents

Élément de pile sèche au manganèse Download PDF

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Publication number
WO2008068929A1
WO2008068929A1 PCT/JP2007/065536 JP2007065536W WO2008068929A1 WO 2008068929 A1 WO2008068929 A1 WO 2008068929A1 JP 2007065536 W JP2007065536 W JP 2007065536W WO 2008068929 A1 WO2008068929 A1 WO 2008068929A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
zinc
positive electrode
manganese
electrode zinc
Prior art date
Application number
PCT/JP2007/065536
Other languages
English (en)
Japanese (ja)
Inventor
Yasuo Mukai
Hiroshi Hase
Original Assignee
Panasonic Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panasonic Corporation filed Critical Panasonic Corporation
Publication of WO2008068929A1 publication Critical patent/WO2008068929A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/148—Lids or covers characterised by their shape
    • H01M50/154—Lid or cover comprising an axial bore for receiving a central current collector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/182—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells with a collector centrally disposed in the active mass, e.g. Leclanché cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/598—Guarantee labels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M2006/5094—Aspects relating to capacity ratio of electrolyte/electrodes or anode/cathode

Definitions

  • the present invention relates to a manganese dry battery, and more particularly to a manganese dry battery provided with a protective member that covers the outer peripheral surface of a negative electrode zinc can.
  • a negative electrode zinc can used for a manganese dry battery serves as both a negative electrode and a container. For this reason, as the discharge reaction progresses, zinc is consumed, the thickness of the side surface of the negative electrode zinc can becomes thin, and holes may be partially opened.
  • Patent Document 1 Japanese Patent Laid-Open No. 6-318451
  • Patent Document 2 JP 2006-19091 A
  • the manganese dry battery of the present invention includes a bottomed cylindrical negative electrode zinc can, a positive electrode mixture contained in the negative electrode zinc can and containing manganese dioxide, carbon powder, and an electrolyte, and the negative electrode zinc can.
  • a separator disposed between the positive electrode mixture and a protective member that covers an outer peripheral surface of the negative electrode zinc can; and zinc contained in the negative electrode zinc can and manganese dioxide contained in the positive electrode mixture;
  • the electric capacity ratio is 2.24 or more and 4.00 or less.
  • the manganese dry battery of the present invention has an electric capacity ratio of zinc contained in the negative electrode zinc can to manganese dioxide contained in the positive electrode mixture (hereinafter simply referred to as electric capacity ratio) of 2.24 or more and 4.00 or less. Therefore, it has a sufficient amount of zinc relative to manganese dioxide, so as the discharge reaction progresses, the zinc is consumed and the thickness of the side surface of the negative electrode zinc can is reduced. Even so, there is no partial opening and it is difficult for the liquid to leak. Therefore, it is not necessary to use the aforementioned metal container, thick layer, and exterior label! /, So that a negative electrode zinc can with a larger outer diameter than before can be used, and the capacity can be increased. It is what you play.
  • 1 is a cross-sectional view of a part of a manganese dry battery R6 according to an embodiment of the present invention.
  • the electric capacity ratio of zinc contained in the negative electrode zinc can to manganese dioxide contained in the positive electrode mixture is set to 2.24 or more and 4.00 or less. This electric capacity ratio is a ratio calculated from the theoretical capacity.
  • the electric capacity ratio is 2.40 or more and 4.00 or less. In this way, there is almost no risk of leakage even if the battery is loaded into the device and used, and if you forget to turn off the switch and remain in the overdischarge state for a long time.
  • the weight ratio of manganese dioxide to carbon powder is preferably 4.0 or more. By doing so, the positive electrode mixture becomes hard, and the mechanical strength of the battery can be maintained even if a thin negative electrode zinc can is used. 4. If it is less than 0, the carbon powder is relatively increased, and the positive electrode mixture is softened and the mechanical strength of the battery may be lowered.
  • a heat-shrinkable resin film having a thickness of 0.03 mm to 0.15 mm may be used for the protective member.
  • a negative electrode zinc can having an outer diameter larger than that of the conventional one can be used, and the capacity can be increased.
  • the protective member is printed, and the printed protective member is often referred to as an exterior label! /.
  • the thickness of the exterior label is less than 0.03 mm, the strength is insufficient and it is easily damaged and if it is thicker than 0.15 mm, the negative electrode zinc can 3 having a substantially larger outer diameter than before should be used. The discharge capacity cannot be increased significantly.
  • FIG. 1 is a front view of a cross section of a part of an AA manganese dry battery R6 according to an embodiment including an exterior label 9.
  • a positive electrode mixture 6 is stored via a separator 7.
  • the negative electrode zinc can 3 is closed by a zinc plate in which only one of the two openings of the cylinder is open and the other is the bottom.
  • the paper 5 is placed on the positive electrode mixture 6, and the sealing body 2 closes the opening of the negative electrode zinc can 3 on the upper side.
  • the positive electrode mixture 6 is a mixture of manganese dioxide as an active material, carbon powder such as acetylene black as a conductive material, and a zinc chloride aqueous solution to which a small amount of ammonium chloride is added as an electrolytic solution.
  • manganese dioxide it is preferable to use electrolytic manganese dioxide that can provide a high discharge capacity. However, since the present invention can provide sufficient discharge performance as compared with the prior art, in consideration of manufacturing costs, Inexpensive natural manganese dioxide or chemical manganese may be used as appropriate.
  • the negative electrode zinc can 3 is preferably made of a zinc alloy added with lead, mangan, magnesium, indium, etc., which preferably has high mechanical strength and excellent corrosion resistance. Yes.
  • the separator 7 is a kraft paper that is coated with a paste obtained by applying, in an alcohol solvent, a cross-linked starch and a binder mainly composed of butyl acetate, and then drying.
  • the separator 7 is disposed so that the coated surface faces and faces the negative electrode zinc can 3.
  • a carbon rod 4 obtained by sintering carbon powder is inserted in the center of the positive electrode mixture 6.
  • a bottom paper 8 is disposed between the bottom of the positive electrode mixture 6 and the bottom of the negative electrode zinc can 3 to ensure insulation. That is, the separator 7 is disposed so as to cover the inner peripheral surface of the cylindrical portion of the negative electrode zinc can 3, and the positive electrode mixture 6 is surrounded by the separator 7, the bottom paper 8, and the backing paper 5.
  • the sealing body 2 is fastened by the outer peripheral edge portion of the positive electrode terminal plate 1 fitted to the top of the carbon rod 4 and the caulking portion of the open end portion of the negative electrode zinc can 3.
  • an external label 9 made of a heat-shrinkable resin is adhered in order to ensure electrical insulation from the outside.
  • the exterior label 9 is at least one selected from the group consisting of polyethylene, polyvinyl chloride, polystyrene, and polyethylene terephthalate. It consists of a heat-shrinkable resin film containing.
  • the negative electrode zinc can 3 is directly covered by heat-shrinking the whole heat-shrinkable resin film with hot air.
  • the outer label 9 becomes the outermost layer of the cylindrical part of the dry cell.
  • the heat-shrinkable resin film is a tube having an end face bonded in advance, and a negative electrode zinc can 3 in which a power generation element is housed and sealed is inserted, and hot air is used.
  • the entire tubular heat-shrinkable resin film may be heat-shrinked.
  • polystyrene, polyethylene, and polyethylene terephthalate are preferable as the heat-shrinkable resin film.
  • the electric capacity ratio between zinc contained in the negative electrode zinc can 3 and mangan dioxide contained in the positive electrode mixture 6 is set to 2.24 or more and 4.00 or less.
  • the electric capacity ratio was calculated by the following method.
  • the positive electrode is obtained by multiplying the weight of the active material manganese dioxide contained in the positive electrode mixture 6 by the theoretical electric capacity (0.308 Ah / g) per unit weight. For example, when 45 g of electrolytic manganese dioxide having a purity of 91% manganese dioxide is contained in 9 g of the positive electrode mixture 6, the following formula is used.
  • the side surface (cylindrical portion) of the negative electrode zinc can 3 facing the positive electrode mixture 6 corresponds to the active material
  • the outer diameter of the negative electrode zinc can 3 corresponds to the thickness of the side surface
  • the height of the positive electrode mixture 6 ( ⁇ Calculate the volume using paper 5 and bottom paper 8), multiply by the density of zinc (7.14 g / cubic centimeter) and convert to weight, and then add zinc purity of negative electrode zinc can 3 and its unit weight It is obtained by multiplying the theoretical electric capacity of (0.820 Ah / g).
  • a negative electrode zinc can 3 with an outer diameter of ⁇ 13.64 mm, a side thickness of 0.3 mm, and a zinc purity of 99.5% is filled with a positive electrode mixture 6 with a height of 38.5 mm! /
  • the case is calculated by the following formula.
  • the thickness of the heat-shrinkable resin film outer packaging label 9 made of polystyrene of each battery was 0.03 mm
  • the outer diameter of the negative electrode zinc can 3 was ⁇ 13.64, which was common to all.
  • the positive electrode was performed in a binary manner by changing the weight ratio of the manganese dioxide to the carbon powder of the mixture 6 in various ways.
  • Electrolytic manganese dioxide having a purity of 91% was used for manganese dioxide, and acetylene black was used for carbon powder.
  • an aqueous solution containing 2% by weight of ammonium chloride and 30% by weight of zinc chloride was used, and a predetermined amount was mixed according to the weight ratio of manganese dioxide to the carbon powder, and a positive electrode mixture
  • the negative electrode zinc can 3 in which the separator 7 and the bottom paper 8 were in close contact with each other was filled so that the height of 6 was 38.5 mm.
  • the negative electrode zinc can 3 was a zinc alloy containing 0.4% of lead, and the zinc purity was 99.5%.
  • Each battery obtained above was discharged with a load of 3.9 ⁇ . The time required to reach a final voltage of 0.9V was measured.
  • the 15 batteries had an electric capacity ratio of 2.24 or more, and the negative electrode capacity was sufficient with respect to the positive electrode capacity. Therefore, all 10 batteries of any No. did not leak. On the other hand, in the experiment number where the capacitance ratio was less than 2.24, one or more of the 10 batteries leaked.
  • the batteries of Nos. 1, 6-8, and 11 14 that have a capacitance ratio of 2.40 or more are used.
  • the electric capacity ratio of the batteries No. 2 and 15 is 2.24 or more but less than 2.40.
  • the discharge sustainability is excellent if the discharge duration is 85 minutes or more. All the batteries of No. 1 15 have a duration longer than 85 minutes, but especially when the capacity ratio approaches 4.0, as in the case of 11 batteries, the balance between leakage resistance and discharge characteristics is balanced. Therefore, the capacitance ratio is preferably 4.0 or less because an excessive negative electrode capacitance causes a shortage of the positive electrode capacitance and it is difficult to obtain a substantial effect of increasing the capacitance.
  • the capacitance ratio is preferably 2.40 or more.
  • the capacity ratio was less than 2.24, and the capacity of the negative electrode was insufficient relative to the capacity of the positive electrode. .
  • batteries with an electric capacity ratio of 2.24 or more have a leak-proof power.
  • the outer labels 9 had a thickness of 0.03 mm force, etc. Nos. 6-10 and 16-25 using a heat shrinkable resin film of 0.15 mm.
  • negative electrode zinc cans 3 having a larger outer diameter than conventional ones can be used, and all are evaluated as having excellent discharge sustainability.
  • the batteries No. 26 and 27 using a heat-shrinkable resin film having a thickness of 0.20 mm for the outer label 9 have a discharge duration of 85 minutes or less and excellent discharge sustainability. I can't say that!
  • the mechanical strength of the negative electrode zinc can 3 decreases, but the mechanical strength decreases due to the hardness of the positive electrode mixture 6 stored in the negative electrode zinc can 3.
  • the effect of the weight ratio of the carbon powder and manganese dioxide in the positive electrode mixture 6 on the impact resistance of the dry cell was examined using the batteries of Experiment Example No. 6-10. It was. The method of checking was to drop the battery from the lm height with the battery side down, and then remove the exterior label 9 and / or visually confirm the presence or absence of dents on the negative electrode zinc can 3.
  • the manganese dry battery of the present invention since the manganese dry battery of the present invention has a leak-proof property and a high discharge capacity, it can be applied to a power source such as a flashlight or a portable electronic device.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Primary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

[PROBLÈMES] Proposer un élément de pile sèche au manganèse qui combine une résistance à la fuite de liquide élevée avec une capacité de décharge élevée. [MOYENS POUR RÉSOUDRE LES PROBLÈMES] L'élément de pile sèche au manganèse a une étiquette de recouvrement (9) formée à partir d'une résine thermorétrécissable, le rapport de la capacité électrique du zinc contenu dans un bac de zinc (3) d'électrode négative sur celle du dioxyde de manganèse contenu dans un mélange (6) d'électrode positive étant régulé de 2,24 à 4,00.
PCT/JP2007/065536 2006-12-05 2007-08-08 Élément de pile sèche au manganèse WO2008068929A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006328663A JP2008140748A (ja) 2006-12-05 2006-12-05 マンガン乾電池
JP2006-328663 2006-12-05

Publications (1)

Publication Number Publication Date
WO2008068929A1 true WO2008068929A1 (fr) 2008-06-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/065536 WO2008068929A1 (fr) 2006-12-05 2007-08-08 Élément de pile sèche au manganèse

Country Status (3)

Country Link
JP (1) JP2008140748A (fr)
CN (1) CN100583518C (fr)
WO (1) WO2008068929A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111864224B (zh) * 2019-11-26 2021-10-15 宁波丰银电池有限公司 一种锌锰干电池制造工艺
CN111933827A (zh) * 2020-06-05 2020-11-13 松栢投资有限公司 一种电池及其制造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0244651A (ja) * 1988-08-01 1990-02-14 Fuji Elelctrochem Co Ltd スパイラル形電池の製造方法
JPH02162652A (ja) * 1988-12-15 1990-06-22 Fuji Elelctrochem Co Ltd 積層乾電池の製造方法
JPH03245466A (ja) * 1990-02-22 1991-11-01 Matsushita Electric Ind Co Ltd 渦巻電極を備えた電池
JPH0511313U (ja) * 1991-07-26 1993-02-12 富士電気化学株式会社 マンガン乾電池
JP2001006635A (ja) * 1999-06-16 2001-01-12 Matsushita Electric Ind Co Ltd マンガン乾電池
JP2001351639A (ja) * 2000-04-03 2001-12-21 Matsushita Electric Ind Co Ltd マンガン乾電池およびその製造方法
JP2004063252A (ja) * 2002-07-29 2004-02-26 Matsushita Electric Ind Co Ltd マンガン乾電池
WO2005045959A1 (fr) * 2003-11-07 2005-05-19 Toshiba Battery Co., Ltd. Materiau actif d'electrode negative pour pile, boitier anode, plaque negative en zinc pour pile, pile seche en manganese et leur procede de fabrication

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0244651A (ja) * 1988-08-01 1990-02-14 Fuji Elelctrochem Co Ltd スパイラル形電池の製造方法
JPH02162652A (ja) * 1988-12-15 1990-06-22 Fuji Elelctrochem Co Ltd 積層乾電池の製造方法
JPH03245466A (ja) * 1990-02-22 1991-11-01 Matsushita Electric Ind Co Ltd 渦巻電極を備えた電池
JPH0511313U (ja) * 1991-07-26 1993-02-12 富士電気化学株式会社 マンガン乾電池
JP2001006635A (ja) * 1999-06-16 2001-01-12 Matsushita Electric Ind Co Ltd マンガン乾電池
JP2001351639A (ja) * 2000-04-03 2001-12-21 Matsushita Electric Ind Co Ltd マンガン乾電池およびその製造方法
JP2004063252A (ja) * 2002-07-29 2004-02-26 Matsushita Electric Ind Co Ltd マンガン乾電池
WO2005045959A1 (fr) * 2003-11-07 2005-05-19 Toshiba Battery Co., Ltd. Materiau actif d'electrode negative pour pile, boitier anode, plaque negative en zinc pour pile, pile seche en manganese et leur procede de fabrication

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Publication number Publication date
JP2008140748A (ja) 2008-06-19
CN100583518C (zh) 2010-01-20
CN101375440A (zh) 2009-02-25

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