WO2006004033A1 - Pile sèche alcaline - Google Patents

Pile sèche alcaline Download PDF

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Publication number
WO2006004033A1
WO2006004033A1 PCT/JP2005/012189 JP2005012189W WO2006004033A1 WO 2006004033 A1 WO2006004033 A1 WO 2006004033A1 JP 2005012189 W JP2005012189 W JP 2005012189W WO 2006004033 A1 WO2006004033 A1 WO 2006004033A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkaline
polybutene
battery
negative electrode
weight
Prior art date
Application number
PCT/JP2005/012189
Other languages
English (en)
Japanese (ja)
Inventor
Yasushi Sumihiro
Seiji Wada
Shinichi Sumiyama
Hiroaki Sato
Original Assignee
Matsushita Electric Industrial Co., Ltd.
Nippon Oil 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 Matsushita Electric Industrial Co., Ltd., Nippon Oil Corporation filed Critical Matsushita Electric Industrial Co., Ltd.
Publication of WO2006004033A1 publication Critical patent/WO2006004033A1/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
    • 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 of a single cell or a single battery
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members

Definitions

  • the present invention relates to an alkaline battery, and more particularly to a sealing agent applied to a sealing portion of an alkaline battery.
  • a sealing agent made of a mixture of asphalt, polybutene, and an organic solvent is applied to the sealing portion of a battery case, sealing plate, and gasket in an alkaline battery, and then dried and heated with It has been proposed to form a sealant coating film by soft melting (for example, Patent Document 1).
  • Asphalt is solid at room temperature, and in order to mix with polybutene and form a uniform coating film of the sealing agent at the sealing portion, it is necessary to dilute the sealing agent with a highly volatile organic solvent. is there. Moreover, after applying this mixture to a sealing part, it must be dried and melted by heating at a high temperature.
  • Patent Document 1 Japanese Patent Laid-Open No. 57-163962
  • an object of the present invention is to provide a highly reliable and low-cost alkaline dry battery having excellent leakage resistance in order to solve the above-described conventional problems.
  • the alkaline dry battery of the present invention includes a positive electrode including at least one of manganese dioxide and nickel oxyhydroxide; a negative electrode including zinc; a separator disposed between the positive electrode and the negative electrode; an alkaline electrolyte; A battery that houses the negative electrode, separator, and alkaline electrolyte A pond case; a sealing plate for sealing the opening of the battery case; a gasket disposed between the battery case and the sealing plate; and a negative electrode current collector inserted into the negative electrode and the gasket.
  • arylalkanes having 13 to 24 carbon atoms at least selected from the group consisting of arylalkanes having 13 to 24 carbon atoms, diarylalkanes having 13 to 24 carbon atoms, and triarylalkane forces having 22 to 24 carbon atoms.
  • It has a sealing agent layer containing one kind of aromatic hydrocarbon and polybutene having an average molecular weight of 700 to 10,000 in a weight ratio of 10:90 to 80:20.
  • diarylalkane is a ferro-ylylethane! /.
  • the triarylalkane is preferably distyrylxylene.
  • the sealing agent layer preferably further contains a colorant in an amount of 0.001 to 5.0 parts by weight per 100 parts by weight of the mixture of the aromatic hydrocarbon and polybutene.
  • the sealing agent since the sealing agent has appropriate fluidity and adhesiveness, the sealing agent can be uniformly applied to the sealing portion between the gasket and the battery case. As a result, a highly reliable alkaline battery excellent in leakage resistance can be obtained.
  • the sealing agent used in the alkaline dry battery of the present invention is a dilution step in which an organic solvent is added to the sealing agent as in the case of a conventional sealing agent that only needs to be applied to the sealing portion, and a drying step in which the organic solvent is skipped. And a melting step for forming a uniform coating film is not required. For this reason, the production efficiency is improved, and a low-cost alkaline battery can be obtained.
  • FIG. 1 is a front view of a cross section of a part of an alkaline battery in an example of the present invention.
  • the alkaline dry battery sealing portion that is, between the gasket and the battery case, is a C 13-24 arylene alkane, a C13-24 dial alkane, and a carbon number.
  • a sealing agent containing at least one aromatic hydrocarbon selected from the group consisting of 22 to 24 triarylalkane forces and polybutene having an average molecular weight of 700 to 10,000 is applied.
  • a 13 to 24 carbon arylene, a 13 to 24 carbon arylene, and A triarylalkane having 22 to 24 carbon atoms is a liquid substance having a relatively low viscosity at room temperature.
  • These aromatic hydrocarbons have excellent compatibility with polybutene, are stable with respect to temperature changes, and have excellent alkali resistance.
  • Polybutene with an average molecular weight of 700-10000 is relatively high in viscosity and has excellent viscosity and adhesion! / Speak.
  • the mixing weight ratio of the above aromatic hydrocarbon and polybutene is 10:90 to 80:20. That is, the weight ratio of polybutene to the above aromatic hydrocarbon is 0.25-9.
  • the sealing agent since the sealing agent has appropriate fluidity and viscosity, a sealing agent layer having excellent sealing properties is formed at the sealing portion, and an alkaline dry battery having excellent leakage resistance can be obtained.
  • the sealing agent used in the alkaline dry battery of the present invention includes a diluting step in which an organic solvent is added to the sealing agent, such as a conventional sealing agent that is simply applied to the sealing portion. Skip The drying process and the melting process to form a uniform coating film are not required. For this reason, the production efficiency can be improved and the manufacturing cost can be reduced.
  • the arylene alkane having 13 to 24 carbon atoms has the chemical formula (1):
  • the diarylalkanes having 13 to 24 carbon atoms include phenolylylethane, chemical formula (4)
  • phenylsilyletan include the following chemical formulas (6 to (15):
  • Diaryl alkanes have a minimum structure of 13 carbons.
  • Examples of the C22-24 triarylalkane include distyrylxylene.
  • distyrylxylene examples include the following chemical formulas (16) to (25): [0027] [Chemical 7]
  • triarylalkanes When the number of carbon atoms in the triarylalkane exceeds 24, the viscosity becomes high and uneven coating tends to occur. In addition, triarylalkanes are structurally minimal when considering starting materials and production processes. The number of carbon atoms is 22.
  • diarylalkanes having 24 or less carbon atoms are described in, for example, US Pat. No. 5,073,655, US Pat. No. 5,866,733, and JP-A-2003-119159.
  • a method is used in which a styrene is reacted with an aromatic compound in the presence of a zeolite catalyst to obtain a diallelic alkane, particularly 1,1-diarylethane.
  • triarylalkanes having 22 to 24 carbon atoms are co-produced by the reaction of diarylalkanes with aromatic compounds and styrenes in the production process.
  • Examples of those containing 1-xylylethane as a main component include “SAS296” manufactured by Shin Nippon Petrochemical Co., Ltd.
  • commercially available triarylalkanes containing distyrylxylene represented by chemical formulas (16) to (19) as a main component include, for example, “SAS” manufactured by Shin Nippon Petrochemical Co., Ltd. — LH ”.
  • Polybutene is a polymer obtained by polymerizing isobutene as a main monomer, and examples thereof include a homopolymer of isobutene and a copolymer of isobutene and n-butene.
  • Polybutene is mainly involved in the shape retention characteristics and sealing properties of the sealant layer formed after applying the sealant of the present invention.
  • the average molecular weight of polybutene can be determined as the number average molecular weight in terms of polystyrene by, for example, measurement by GPC (gel permeation chromatography).
  • Polybutene can be used in a single type. Use a combination of two or more types.
  • the above-mentioned sealant which is a mixture of aromatic hydrocarbon and polybutene is colorless and transparent. In order to make it easy to confirm the application state of the sealant, it is preferable to add 0.001 to 5.0 parts by weight of the colorant per 100 parts by weight of the mixture of aromatic hydrocarbon and polybutene.
  • Additive power of coloring agent When the amount is less than 0.001 part by weight per 100 parts by weight of the mixture of aromatic hydrocarbon and polybutene, coloring of the sealant becomes insufficient. On the other hand, the amount of colorant added Strength If it exceeds 5.0 parts by weight per 100 parts by weight of the mixture of aromatic hydrocarbon and polybutene, the sealant will have insufficient leakage resistance.
  • an azo compound As the colorant, an azo compound, carbon black, or titanium oxide is used.
  • Example 1 fuel heptane represented by the chemical formula (1) (product number 56832-12, manufactured by Kanto Chemical Co., Ltd.) was used as an arylene alkane having 13 carbon atoms.
  • Example 2 1-phenyldecane (product number 11130-41 manufactured by Kanto Chemical Co., Ltd.) represented by the chemical formula (2) was used as an arylalkane having 16 carbon atoms.
  • Example 3 1-phenyloctadecane (product number 12470-1A manufactured by Kanto Chemical Co., Ltd.) represented by the chemical formula (3) was used as an arylalkane having 24 carbon atoms.
  • the chemical formula (27) is an arylene alkane having 26 carbon atoms: [0038] [Chemical 9]
  • Manganese diacid and graphite were mixed in a weight ratio of 90:10. Then, this mixture was mixed with a 40% by weight potassium hydroxide aqueous solution as an alkaline electrolyte in a weight ratio of 100: 3, sufficiently stirred, and then compressed into a flake shape. Next, the flaky positive electrode mixture was pulverized into granules, classified by a sieve, and 10-: LOO mesh was pressure-formed into a hollow cylinder to obtain a pellet-like positive electrode mixture.
  • Sodium gel acrylate as a gelling agent, 40 wt% potassium hydroxide aqueous solution as an alkaline electrolyte, and zinc powder as a negative electrode active material are mixed in a weight ratio of 1:33:66 to form a gel negative electrode. Obtained.
  • FIG. 1 is a front view of a cross section of a part of a cylindrical alkaline battery.
  • the negative electrode current collector 6 was inserted into the center of the gelled negative electrode 3.
  • the negative electrode current collector 6 was integrated with a gasket 5 and a bottom plate (sealing plate) 7 that also served as a negative electrode terminal.
  • battery cables The opening end of the battery case 1 was pressed against the peripheral edge of the bottom plate 7 through the end of the resin gasket 5 to seal the opening of the battery case 1.
  • the outer surface of the battery case 1 was covered with an outer label 8.
  • 50 parts by weight of polyamide, 35 parts by weight of xylene and 15 parts by weight of butanol were diluted and applied to the portion of gasket 5 that was in close contact with negative electrode current collector 6 and dried to provide gasket 5 and negative electrode.
  • the space between the current collectors 6 was sealed.
  • Pitch, polybutene having an average molecular weight of 1000, and toluene were mixed at a weight ratio of 40:20:40 to obtain a sealant.
  • This sealant was applied to the part of the battery case that was in close contact with the gasket, then dried and heated and melted at about 150 ° C. to form a coating film.
  • An alkaline battery was produced in the same manner as in Example 1 except that the sealing agent was used for sealing.
  • Example 4 “SAS296” manufactured by Nippon Petrochemical Co., Ltd. was used as a gialylalkane mainly composed of 1-fluoro-l-xylylethane represented by chemical formulas (6) to (10). It was.
  • a diarylalkane having 26 carbon atoms has the chemical formula (28):
  • each alkaline dry battery was prepared in the same manner as in Example 1, except that various triarylalkanes having different carbon numbers shown in Table 3 were used instead of 1-heptane. It produced and the heat cycle test was done.
  • Example 5 “SAS-LH” manufactured by Nippon Petrochemical Co., Ltd. was used as a triarylalkane mainly composed of distyrylxylene represented by chemical formulas (16) to (19).
  • Comparative Example 5 as a triarylalkane having 26 carbon atoms, chemical formula (29):
  • alkaline dry batteries were prepared in the same manner as in Example 4 except that polybutenes having different average molecular weights shown in Table 4 were used instead of polybutenes having an average molecular weight of 1000, and heat cycle tests were conducted. went. The results are shown in Table 4.
  • the average molecular weight of polybutene was determined by gel permeation chromatography using a Waters 2690 separation module and a Waters 2410 refractive index detector.
  • Example 7 3000 0 0 0
  • Example 8 10000 0 0 0
  • Table 5 shows the mixing weight ratio of ⁇ SAS296 '' manufactured by Nippon Petrochemical Co., Ltd. as a diarylalkane mainly composed of 1-fluoro-l-xylylethane and polybutene having an average molecular weight of 1000 in the preparation of the sealant.
  • Alkaline batteries were produced in the same manner as in Example 4 except for the changes as shown, and subjected to a heat cycle test. The results are shown in Table 5.
  • a positive electrode mixture was prepared in the same manner as in Example 1, except that a mixture of diacid / manganese and oxyhydroxide / nickel in a weight ratio of 1: 1 was used as the positive electrode active material.
  • Alkaline dry batteries were produced in the same manner as in Example 4 and Comparative Example 4 except that this positive electrode mixture was used, and a heat cycle test was conducted. The results are shown in Table 8.
  • Example 1 SAS296 13-24 0 0 0 Comparative Example 1 0 1,1-Dixylyldecane 26 0 5 7
  • the alkaline dry battery of the present invention is suitably used as a power source for electronic devices such as portable devices and information devices.

Abstract

On décrit une cellule sèche alcaline comprenant une couche d’étanchéité entre un joint d’étanchéité et un boîtier de pile. La couche d’étanchéité contient au moins un hydrocarbure aromatique choisi dans le groupe consistant en arylalcanes comportant de 13 à 24 atomes de carbone, des diarylalcanes comportant de 13 à 24 atomes de carbone et des triarylalcanes comportant de 22 à 24 atomes de carbone, et un polybutène ayant un poids moléculaire de 700 à 10 000 dans un rapport pondéral de 10/90 à 80/20. La cellule sèche alcaline présente une excellente résistance à la fuite et une fiabilité élevée et peut être produite à faible coût.
PCT/JP2005/012189 2004-07-02 2005-07-01 Pile sèche alcaline WO2006004033A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-196923 2004-07-02
JP2004196923A JP2006019178A (ja) 2004-07-02 2004-07-02 アルカリ乾電池

Publications (1)

Publication Number Publication Date
WO2006004033A1 true WO2006004033A1 (fr) 2006-01-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008097965A (ja) * 2006-10-11 2008-04-24 Matsushita Electric Ind Co Ltd アルカリ一次電池
US11817591B2 (en) 2020-05-22 2023-11-14 Duracell U.S. Operations, Inc. Seal assembly for a battery cell

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG183720A1 (en) 2005-08-12 2012-09-27 Cambrios Technologies Corp Nanowires-based transparent conductors
JP5255877B2 (ja) * 2008-03-25 2013-08-07 Ｆｄｋエナジー株式会社 密閉型電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6017855A (ja) * 1983-07-12 1985-01-29 Fuji Elelctrochem Co Ltd 小型電池
JPH07130340A (ja) * 1993-11-04 1995-05-19 Toshiba Battery Co Ltd アルカリマンガン乾電池
JP5058219B2 (ja) * 2009-06-30 2012-10-24 日本電信電話株式会社 シナリオ作成方法、その装置、プログラム及び記録媒体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6017855A (ja) * 1983-07-12 1985-01-29 Fuji Elelctrochem Co Ltd 小型電池
JPH07130340A (ja) * 1993-11-04 1995-05-19 Toshiba Battery Co Ltd アルカリマンガン乾電池
JP5058219B2 (ja) * 2009-06-30 2012-10-24 日本電信電話株式会社 シナリオ作成方法、その装置、プログラム及び記録媒体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008097965A (ja) * 2006-10-11 2008-04-24 Matsushita Electric Ind Co Ltd アルカリ一次電池
EP2075861A1 (fr) * 2006-10-11 2009-07-01 Panasonic Corporation Batterie alcaline primaire
EP2075861A4 (fr) * 2006-10-11 2012-03-07 Panasonic Corp Batterie alcaline primaire
US8247108B2 (en) 2006-10-11 2012-08-21 Panasonic Corporation Alkaline primary battery comprising a sealing agent
US11817591B2 (en) 2020-05-22 2023-11-14 Duracell U.S. Operations, Inc. Seal assembly for a battery cell

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