JP2003272636A - Alkaline battery - Google Patents
Alkaline batteryInfo
- Publication number
- JP2003272636A JP2003272636A JP2002070453A JP2002070453A JP2003272636A JP 2003272636 A JP2003272636 A JP 2003272636A JP 2002070453 A JP2002070453 A JP 2002070453A JP 2002070453 A JP2002070453 A JP 2002070453A JP 2003272636 A JP2003272636 A JP 2003272636A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- cup
- positive electrode
- copper
- alkaline battery
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 230000002093 peripheral effect Effects 0.000 claims description 9
- 238000007772 electroless plating Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052753 mercury Inorganic materials 0.000 abstract description 9
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 36
- 229910052718 tin Inorganic materials 0.000 description 36
- 239000011247 coating layer Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000000873 masking effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 102100031083 Uteroglobin Human genes 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- 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
- H01M50/155—Lids or covers characterised by the material
- H01M50/157—Inorganic material
- H01M50/159—Metals
-
- 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
- H01M50/155—Lids or covers characterised by the material
- H01M50/164—Lids or covers characterised by the material having a layered structure
-
- 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
- H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
- H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Primary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、偏平型構成による
コイン型アルカリ電池あるいはボタン型アルカリ電池に
適用して好適なアルカリ電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline battery suitable for application to a coin type alkaline battery or a button type alkaline battery having a flat structure.
【０００２】[0002]
【従来の技術】電子腕時計、携帯用電子計算機等の小型
電子機器に使用されるコイン型あるいはボタン型のアル
カリ電池は、図３にその概略断面図を示すように、正極
缶１の開口端が、断面Ｌ字状のガスケット２を介して負
極カップ３によって封止される。負極カップ３は、その
開口端縁に断面Ｕ字状に外周面に沿って折り返された折
り返し部１３が形成され、この折り返し部１３におい
て、断面Ｌ字状のガスケット２を介して正極缶１の開口
端縁の内周面によって締めつけられて密封保持される。2. Description of the Related Art A coin-type or button-type alkaline battery used in a small electronic device such as an electronic wrist watch or a portable electronic computer has a positive electrode can 1 with an open end as shown in the schematic sectional view of FIG. , And is sealed by the negative electrode cup 3 via the gasket 2 having an L-shaped cross section. The negative electrode cup 3 is provided with a folded-back portion 13 which is folded back along the outer peripheral surface in a U-shaped cross-section at the opening edge thereof. The inner peripheral surface of the opening edge is tightened and hermetically held.
【０００３】この負極カップ３は、ニッケルより成る外
表面層３１と、ステンレス（ＳＵＳ）よりなる金属層３
２と、銅よりなる集電体層３３との３層クラッド材が段
部を有するカップ状にプレス加工されて構成される。The negative electrode cup 3 has an outer surface layer 31 made of nickel and a metal layer 3 made of stainless steel (SUS).
A two-layer clad material including 2 and a current collector layer 33 made of copper is pressed into a cup shape having a step.
【０００４】正極缶１内には、酸化銀もしくは二酸化マ
ンガンを正極活物質とする正極合剤４が収容され、負極
カップ３内には、正極合剤４とセパレータ５を介して水
銀を含まない亜鉛または亜鉛合金粉末を負極活物質とす
る負極合剤６が配置され、アルカリ電解液が注入されて
成る。A positive electrode mixture 4 containing silver oxide or manganese dioxide as a positive electrode active material is accommodated in the positive electrode can 1, and mercury is not contained in the negative electrode cup 3 via the positive electrode mixture 4 and the separator 5. A negative electrode mixture 6 containing zinc or zinc alloy powder as a negative electrode active material is placed and an alkaline electrolyte is injected.
【０００５】負極合剤６は、亜鉛または亜鉛合金粉末に
水銀をアマルガム化した汞化亜鉛を使用することによ
り、亜鉛または亜鉛合金粉末から発生する水素ガス（Ｈ
2 ）、更に亜鉛または亜鉛合金粉末が、負極カップの集
電体層３３の銅とアルカリ電解液を介して接触すること
によってこの集電体から発生する水素ガス（Ｈ2 ） を
抑制するようにしている。The negative electrode mixture 6 is a hydrogen gas (H 2) generated from zinc or zinc alloy powder by using zinc fluoride containing zinc or zinc alloy powder with amalgamated mercury.
2 ) In addition, zinc or zinc alloy powder suppresses hydrogen gas (H 2 ) generated from the current collector by contacting copper of the current collector layer 33 of the negative electrode cup via the alkaline electrolyte. ing.
【０００６】この水素ガス発生の反応は、亜鉛または亜
鉛合金粉末がアルカリ電解液に溶解して起こる反応であ
り、亜鉛は酸化されて酸化亜鉛に変化するものである。
これに対し、上述したように、水銀によりアマルガム化
された汞化亜鉛を使用することによって、水素発生の抑
制を行うことができ、これによってこの水素発生に伴う
容量保存性の低下、内圧の上昇による耐漏液性の低下、
電池の膨れをそれぞれ抑制する効果を得ることができ
る。This reaction of hydrogen gas generation is a reaction that occurs when zinc or zinc alloy powder is dissolved in an alkaline electrolyte, and zinc is oxidized to change to zinc oxide.
On the other hand, as described above, by using zinc aluminide which has been amalgamated with mercury, hydrogen generation can be suppressed, whereby the capacity storage stability and the internal pressure increase due to this hydrogen generation can be suppressed. Decrease in liquid leakage resistance due to
The effect of suppressing the swelling of the battery can be obtained.
【０００７】[0007]
【発明が解決しようとする課題】ところが、近年、環境
問題から、これらコイン型あるいはボタン型のアルカリ
電池においても、水銀の使用をできるだけ回避する方向
にあって、水銀の使用を回避するための多くの研究がな
されている。However, in recent years, due to environmental problems, even in these coin-type or button-type alkaline batteries, there is a tendency to avoid the use of mercury as much as possible, and there are many ways to avoid the use of mercury. Is being researched.
【０００８】例えばアルカリ電解液中の亜鉛または亜鉛
合金粉末からの水素ガスの発生を抑える方法として、水
素過電圧の高い金属を亜鉛粉に合金として添加する方法
や、アルカリ電解液に水素発生を抑制するいわゆるイン
ヒビターを添加する方法が提案されている。しかしなが
ら、これらの方法によっても、亜鉛または亜鉛合金粉末
が集電体とアルカリ電解液を介して接触することにより
発生する水素ガスを完全に抑えることができない。For example, as a method of suppressing the generation of hydrogen gas from zinc or zinc alloy powder in an alkaline electrolyte, a method of adding a metal having a high hydrogen overvoltage as an alloy to zinc powder, or suppressing the generation of hydrogen in an alkaline electrolyte. A method of adding a so-called inhibitor has been proposed. However, even by these methods, the hydrogen gas generated by the zinc or zinc alloy powder coming into contact with the current collector through the alkaline electrolyte cannot be completely suppressed.
【０００９】この水素ガスの発生を効果的に抑えるため
に、図４に示すように、この集電体の銅よりも水素過電
圧の高い金属であるスズ、インジウム、ビスマスの１種
あるいは１種以上の合金より成る被覆層３０を被着する
方法の提案がなされている。この被覆層３０は、無電解
メッキやバレルメッキなどで、上述したスズ、インジウ
ム、ビスマスやこれらの合金を被着することによって形
成され、負極カップ３の内表面に全面的に形成される。
図４において、図３と対応する部分には同一符号を付し
て重複説明を省略する。In order to effectively suppress the generation of this hydrogen gas, as shown in FIG. 4, one or more of tin, indium and bismuth, which are metals having a hydrogen overvoltage higher than that of copper of the current collector, are used. There has been proposed a method of depositing the coating layer 30 made of the above alloy. The coating layer 30 is formed by depositing the above-mentioned tin, indium, bismuth, or an alloy thereof by electroless plating or barrel plating, and is entirely formed on the inner surface of the negative electrode cup 3.
4, parts corresponding to those in FIG. 3 are designated by the same reference numerals, and redundant description will be omitted.
【００１０】この被覆層３０の形成によって水素ガスの
発生は効果的に回避されるものの、この種の被覆層３０
は、銅による集電体層に比しアルカリ電解液の這い上が
り、すなわちクリープ現象が生じ易いことが判明した。
このため、例えば何らかの原因で水素ガスが発生して電
池内の内圧が上昇した場合、正極缶１の開口端と負極カ
ップ３との間の封止部から電解液が漏出するおそれが生
じる。Although the generation of hydrogen gas is effectively avoided by the formation of the coating layer 30, this type of coating layer 30 is used.
It was found that the creeping phenomenon of the alkaline electrolyte, that is, the creep phenomenon, is more likely to occur than in the collector layer made of copper.
For this reason, for example, if hydrogen gas is generated for some reason and the internal pressure in the battery rises, the electrolytic solution may leak from the sealing portion between the open end of the positive electrode can 1 and the negative electrode cup 3.
【００１１】このような不都合を回避するために、図５
に、断面図を示すように、この被覆層３４を、負極カッ
プ３のＵ字状折り返し部１３の折り返し底部１３ａとこ
れよりの外周折り返し部１３ｂとを除いて限定的に負極
カップ内面に形成して、上述したクリープの問題の解決
を図った。In order to avoid such an inconvenience, FIG.
As shown in the cross-sectional view, the coating layer 34 is formed on the inner surface of the negative electrode cup in a limited manner except for the folded back portion 13a of the U-shaped folded portion 13 of the negative electrode cup 3 and the outer circumferential folded portion 13b. Then, the above-mentioned problem of creep was solved.
【００１２】この図５において、図３に対応する部分に
は同一符号を付して重複説明は省略する。In FIG. 5, parts corresponding to those in FIG. 3 are designated by the same reference numerals, and duplicate description will be omitted.
【００１３】この図５においては、このクリープ現象の
問題の解決を図ることができるが、この図５においては
断面Ｌ字状のガスケット２を使用しており、負極カップ
３の内面の被覆層３４による被覆にばらつきがある場合
には負極カップ３の折り返し底部１３ａ近傍の集電体
（銅）層３３とアルカリ電解液とが接するので、この部
分での負極活物質である亜鉛の腐食反応が進行し、耐漏
液性の低下及び容量保存性低下が発生する不都合があっ
た。Although the problem of the creep phenomenon can be solved in FIG. 5, the gasket 2 having an L-shaped cross section is used in FIG. 5, and the coating layer 34 on the inner surface of the negative electrode cup 3 is used. If there is variation in the coating due to, the current collector (copper) layer 33 near the folded bottom portion 13a of the negative electrode cup 3 and the alkaline electrolyte are in contact with each other, so that the corrosion reaction of zinc, which is the negative electrode active material, proceeds at this portion. However, there is a disadvantage that the liquid leakage resistance and the capacity storage stability are deteriorated.
【００１４】本発明は、斯る点に鑑み水銀を使用しない
アルカリ電池において、クリープ現象問題を解決すると
共に耐漏液性及び容量保存性の低下を改善することを目
的とする。In view of the above points, the present invention has an object to solve the problem of creep phenomenon and to improve the deterioration of the leakage resistance and the storage stability of the capacity in a mercury-free alkaline battery.
【００１５】[0015]
【課題を解決するための手段】本発明アルカリ電池は、
酸化銀もしくは二酸化マンガンを正極活物質とする正極
合剤が配された正極缶と、亜鉛又は亜鉛合金粉末を負極
活物質とする負極合剤が配され、開口端縁が断面Ｕ字状
に外周面に沿って折り返し部及び折り返し底部を有し、
内面が銅より成る負極カップとをガスケットを介して密
封すると共にこの正極合剤とこの負極合剤との間にセパ
レータを配し、アルカリ電解液を注入したアルカリ電池
において、この負極カップのこの折り返し部及び折り返
し底部を含まない内面領域に銅よりも水素過電圧の高い
金属もしくは合金を成膜すると共にこのガスケットの先
端がこの負極カップの内面に接触するようにしたもので
ある。The alkaline battery of the present invention comprises:
A positive electrode can in which a positive electrode mixture containing silver oxide or manganese dioxide as a positive electrode active material is arranged, and a negative electrode mixture containing zinc or zinc alloy powder as a negative electrode active material are arranged, and an opening edge has a U-shaped outer periphery. Has a folded back portion and a folded back portion along the surface,
In an alkaline battery in which a negative electrode cup whose inner surface is made of copper is hermetically sealed via a gasket, a separator is placed between the positive electrode mixture and the negative electrode mixture, and an alkaline electrolyte is injected, the folded back of the negative electrode cup The metal or alloy having a higher hydrogen overvoltage than copper is formed on the inner surface region not including the portion and the folded bottom portion, and the tip of the gasket is brought into contact with the inner surface of the negative electrode cup.
【００１６】本発明によれば、負極カップのこの折り返
し部及び折り返し底部を含まない内面領域に銅よりも水
素過電圧の高い金属もしくは合金を成膜したので、アル
カリ電解液のクリープ現象を抑制できると共にガスケッ
トの先端が負極カップの内面に接触するようにしたので
耐漏液性が改善され、且つ負極カップの内面領域の銅よ
りも水素過電圧の高い金属もしくは合金の成膜にばらつ
きがあっても負極カップの非成膜部分にアルカリ電解液
が接しないようにすることができ、負極活物質である亜
鉛の腐食を抑制でき容量保存性の低下を改善できる。According to the present invention, since a metal or an alloy having a hydrogen overvoltage higher than that of copper is deposited on the inner surface region of the negative electrode cup which does not include the folded back portion and the folded back bottom portion, the creep phenomenon of the alkaline electrolyte can be suppressed. Since the tip of the gasket contacts the inner surface of the negative electrode cup, liquid leakage resistance is improved, and even if there is variation in the film formation of a metal or alloy having a hydrogen overvoltage higher than that of copper in the inner surface region of the negative electrode cup, the negative electrode cup It is possible to prevent the alkaline electrolyte from coming into contact with the non-film-forming portion, and it is possible to suppress corrosion of zinc, which is the negative electrode active material, and improve the deterioration of capacity storage stability.
【００１７】[0017]
【発明の実施の形態】以下、図１を参照して本発明アル
カリ電池の実施の形態の例を説明する。図１例は偏平型
のコイル型ないしはボタン型のアルカリ電池の概略断面
図を示し、本例においては、正極缶１の開口端が断面Ｊ
字状ガスケット２０を介して負極カップ３によって封止
される。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the alkaline battery of the present invention will be described below with reference to FIG. FIG. 1 shows a schematic cross-sectional view of a flat type coil type or button type alkaline battery, and in this example, the open end of the positive electrode can 1 has a cross section J.
It is sealed by the negative electrode cup 3 via the letter-shaped gasket 20.
【００１８】この正極缶１は、ステンレススチール板に
ニッケルメッキを施した構成とされ、正極端子を兼ねた
構成とされる。この正極缶１内には酸化銀もしくは二酸
化マンガンを正極活物質とした正極合剤４が、コイン状
もしくはボタン状に成形されたペレットとして収容配置
される。The positive electrode can 1 has a structure in which a stainless steel plate is plated with nickel and also serves as a positive electrode terminal. A positive electrode mixture 4 containing silver oxide or manganese dioxide as a positive electrode active material is housed and arranged in the positive electrode can 1 as pellets formed in a coin shape or a button shape.
【００１９】そして、この正極缶１内の正極合剤４上
に、セパレータ５を配置する。このセパレータ５は、例
えば不織布、セロファン、ポリエチレンをグラフト重合
した膜の３層構造とする。そして、セパレータ５に、ア
ルカリ電解液を含浸させる。アルカリ電解液としては、
例えば水酸化ナトリウム水溶液、あるいは水酸化カリウ
ム水溶液を用いることができる。Then, the separator 5 is placed on the positive electrode mixture 4 in the positive electrode can 1. The separator 5 has a three-layer structure of, for example, a nonwoven fabric, cellophane, and a film obtained by graft-polymerizing polyethylene. Then, the separator 5 is impregnated with the alkaline electrolyte. As an alkaline electrolyte,
For example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution can be used.
【００２０】本例においては、正極缶１の開口端縁の内
周面に例えばナイロン製のリング状の断面Ｊ字状ガスケ
ット２０を配置する。そして、この断面Ｊ字状ガスケッ
ト２０内のセパレータ５上に、負極合剤６を配置する。
この負極合剤６は、非含有水銀すなわち、水銀を含まな
い亜鉛または亜鉛合金粉末とアルカリ電解液、増粘剤等
からなるジェル状をなす。In this example, a ring-shaped J-shaped gasket 20 made of nylon, for example, is arranged on the inner peripheral surface of the opening edge of the positive electrode can 1. Then, the negative electrode mixture 6 is arranged on the separator 5 in the J-shaped gasket 20 in cross section.
The negative electrode mixture 6 is in the form of a gel containing non-containing mercury, that is, mercury-free zinc or zinc alloy powder, an alkaline electrolyte, a thickener, and the like.
【００２１】この負極合剤６を収容するように、正極缶
１の開口端縁内に、負極カップ３を挿入する。この負極
カップ３は、その開口端縁に断面Ｕ字状に外周面に沿っ
て折り返されたＵ字状折り返し部１３が形成され、この
Ｕ字状折り返し部１３において、断面Ｊ字状ガスケット
２０を介して正極缶１の開口端縁の内周面によって締め
つけられて密封保持される。The negative electrode cup 3 is inserted into the opening edge of the positive electrode can 1 so as to accommodate the negative electrode mixture 6. The negative electrode cup 3 has a U-shaped folded-back portion 13 which is folded back along the outer peripheral surface in a U-shaped cross-section along the outer peripheral surface at the opening edge thereof, and the J-shaped cross-section gasket 20 is provided in the U-shaped folded-back portion 13. The positive electrode can 1 is clamped by the inner peripheral surface of the opening edge of the positive electrode can 1 and is hermetically held.
【００２２】この負極カップ３は、ニッケル外表面層３
１と、ステンレス金属層３２と、銅よりなる集電体層３
３との３層クラッド材に、その集電体層３３上に、銅よ
り水素過電圧の高いスズを、メッキしてスズ被覆層３４
が被着された板材を形成し、これを、スズ被覆層３４側
を内側にして段部を有するカップ状にプレス加工して構
成することができる。この場合のスズ被覆層３４は、メ
ッキによるほか、蒸着、スパッタリングによって形成す
ることもできる。This negative electrode cup 3 has a nickel outer surface layer 3
1, a stainless metal layer 32, and a current collector layer 3 made of copper
On the current collector layer 33, tin having a higher hydrogen overvoltage than copper is plated on the three-layer clad material of No. 3 and tin coating layer 34.
It is possible to form a plate material to which is adhered, and press-work this into a cup shape having a step portion with the tin coating layer 34 side inside. In this case, the tin coating layer 34 can be formed not only by plating but also by vapor deposition or sputtering.
【００２３】あるいは、上述した３層クラッド材を、集
電体層３３を内側にしてカップ状にプレス加工して後
に、カップ内にスズの無電解メッキ液を滴下して流延被
着することによってスズ被覆層３４を形成することによ
って負極カップ３を形成することもできる。また、同様
にカップ状プレス加工の後に、スズ被覆層３４を蒸着、
スパッタリングによって形成することもできる。Alternatively, the above-mentioned three-layer clad material is pressed into a cup shape with the current collector layer 33 inside, and then electroless plating solution of tin is dropped into the cup and cast-coated. It is also possible to form the negative electrode cup 3 by forming the tin coating layer 34 with. Similarly, after the cup-shaped press working, the tin coating layer 34 is vapor-deposited,
It can also be formed by sputtering.
【００２４】この負極カップ３におけるスズ被覆層３４
は、負極カップ３のＵ字状折り返し部１３の折り返し底
部１３ａと、これよりの外周折り返し部１３ｂとを除い
て負極カップ３の内面の限定された領域に形成する。こ
のスズ被覆層３４の形成は、その形成時点で、上述した
限定された領域に、限定的に形成することもできるし、
全領域に形成して後、不要部分をエッチング等によって
排除あるいは剥離することによって限定された領域に形
成することもできる。The tin coating layer 34 in the negative electrode cup 3
Is formed in a limited area on the inner surface of the negative electrode cup 3 except for the folded back portion 13a of the U-shaped folded portion 13 of the negative electrode cup 3 and the outer circumferential folded portion 13b. The formation of the tin coating layer 34 can be limitedly formed in the above-described limited region at the time of formation thereof.
After forming in the entire region, unnecessary portions may be removed or peeled off by etching or the like to form in the limited region.
【００２５】スズ被覆層３４の厚さは、０．１０μｍ〜
１００μｍに選定することが好ましい。これは、０．１
０μｍ未満の厚さでは、このスズ被覆層３４に、ピンホ
ールが発生することが考えられるなど、集電体層３３を
確実に被覆することができない場合が生じ、信頼性に問
題が生じるおそれがあることにより、また、１００μｍ
を越えるとこのスズ被覆層３４の効果の差がない上に、
その形成に長時間と、コスト高を来し、また、電池内の
容積の低下を来すなど、なんらその膜厚を大きくするこ
とによる特段の利益が生じないことによる。The thickness of the tin coating layer 34 is from 0.10 μm to
It is preferable to select 100 μm. This is 0.1
If the thickness is less than 0 μm, the tin coating layer 34 may not be able to be reliably coated with the current collector layer 33 due to the possibility that pinholes may be generated, which may cause a problem in reliability. By being 100 μm
If it exceeds, there is no difference in the effect of the tin coating layer 34, and
This is because it takes a long time to form the film, the cost is high, and the volume in the battery is reduced. Therefore, no particular advantage is caused by increasing the film thickness.
【００２６】また本例においては、この断面Ｊ字状ガス
ケット２０の負極カップ３内の先端をこの負極カップ３
の段部の内面に接触する如くし、負極カップ３の内面の
スズ被覆層３４のない部分にアルカリ電解液が接するお
それがない如くする。Further, in this embodiment, the tip of the gasket 20 having a J-shaped cross section inside the negative electrode cup 3 is connected to the negative electrode cup 3.
The inner surface of the stepped portion is contacted with the alkaline electrolytic solution so as not to contact the inner surface of the negative electrode cup 3 where the tin coating layer 34 is not present.
【００２７】次に、本発明の実施例及び比較例を挙げて
更に説明する。
〔実施例１〕この場合、図１で示した構造のＳＲ６２６
ＳＷ電池を構成した。先ず、図２に示すように、上述し
たニッケル外表面層３１と、ステンレス（ＳＵＳ３０
４）による金属層３２と、銅による集電体層３３との３
層による厚さ０．２ｍｍの３層クラッド材４０を用意し
た。このクラッド材４０に、位置決め用孔４１を穿設す
る。この位置決め用孔４１は、後述するマスキングテー
プへの透孔の穿設に際しての位置決めと、負極カップの
プレス加工時の位置決めに用いられるものである。クラ
ッド材４０の、銅による集電体層３３側の面に、マスキ
ングテープ４２を貼着した。次に、このマスキングテー
プ４２に直径５．５ｍｍの円形状の透孔４３を９ｍｍピ
ッチで穿設した。このマスキングテープ４２を、メッキ
マスクとして、その透孔４３を通じて外部に露呈した、
クラッド材４０の集電体層３３上に、限定的に、スズの
無電解メッキを行って、厚さ０．１５μｍの円形状のス
ズ被覆層３４を形成した。その後、純水での洗浄処理を
行って後、エアー乾燥を行い、マスキングテープ４２を
剥離排除し、更に、仕上げ洗浄を行い、乾燥した。この
ようにしてクラッド材４０の銅よりなる集電体層上の選
択された位置に、スズ被覆層３４を点在して形成した。Next, examples and comparative examples of the present invention will be further described. Example 1 In this case, the SR626 having the structure shown in FIG.
A SW battery was constructed. First, as shown in FIG. 2, the nickel outer surface layer 31 and the stainless steel (SUS30
3 of the metal layer 32 of 4) and the collector layer 33 of copper
A three-layer clad material 40 having a thickness of 0.2 mm was prepared. A positioning hole 41 is formed in the clad material 40. The positioning hole 41 is used for positioning when forming a through hole in a masking tape described later and for positioning during pressing of the negative electrode cup. A masking tape 42 was attached to the surface of the clad material 40 on the side of the current collector layer 33 made of copper. Next, the masking tape 42 was provided with circular through holes 43 having a diameter of 5.5 mm at a pitch of 9 mm. The masking tape 42 was exposed to the outside through the through hole 43 as a plating mask.
On the current collector layer 33 of the clad material 40, tin electroless plating was limitedly performed to form a circular tin coating layer 34 having a thickness of 0.15 μm. After that, a cleaning treatment with pure water was performed, and then air drying was performed to remove the masking tape 42 by peeling, and further, final cleaning was performed and drying was performed. In this way, tin coating layers 34 were formed in a scattered manner at selected positions on the copper current collector layer of the clad material 40.
【００２８】このクラッド材４０の、各スズ被覆層３４
が形成された部分を、打ち抜きプレス加工することによ
って、図１で説明した周縁にＵ字状折り返し部１３が形
成され、その折り返し底部１３ａと、外周折り返し部１
３ｂを除いて内面にスズ被覆層３４が形成された負極カ
ップ３を成形した。Each tin coating layer 34 of the clad material 40
The U-shaped folded-back portion 13 is formed on the periphery described with reference to FIG. 1 by punching and pressing the portion in which the U-shaped portion is formed, and the folded-back bottom portion 13a and the outer peripheral folded-back portion 1 are formed.
A negative electrode cup 3 having a tin coating layer 34 formed on the inner surface except for 3b was molded.
【００２９】一方、２８重量％の水酸化ナトリウム水溶
液のアルカリ電解液を注入し、次に正極合剤４をディス
ク状に成形したペレットを、前述した正極缶１内に挿入
して、正極合剤４にアルカリ電解液を吸収させる。On the other hand, a 28 wt% sodium hydroxide aqueous solution of an alkaline electrolyte was injected, and then the positive electrode mixture 4 was molded into a disk-shaped pellet. 4. Absorb alkaline electrolyte.
【００３０】この正極合剤４によるペレット上に、不織
布、セロファン、ポリエチレンをグラフト重合した膜の
３層構造の円形状に打ち抜いたセパレータ５を装填し、
このセパレータ５に、２８重量％の水酸化ナトリウム水
溶液のアルカリ電解液を滴下して含浸させた。A separator 5 punched in a circular shape having a three-layer structure of a non-woven fabric, cellophane, and a film obtained by graft-polymerizing polyethylene was loaded on the pellet of the positive electrode mixture 4,
The separator 5 was impregnated with an alkaline electrolyte of 28% by weight sodium hydroxide aqueous solution.
【００３１】このセパレータ５上に、水銀を含まないア
ルミニウム、インジウム、ビスマスを含む亜鉛合金粉、
増粘剤、水酸化ナトリウム水溶液から成るジェル状の負
極合剤６を載置し、この負極合剤６を覆って負極カップ
３を、正極缶１の開口端縁内に、６６ナイロンに６１０
ナイロンを塗布して成るナイロン製リング状の断面Ｊ字
状ガスケット２０を介して挿入し、スエージ（横締め）
してかしめつけて密封してアルカリ電池を作製した。こ
の場合、断面Ｊ字状ガスケット２０の負極カップ３内の
先端がこの負極カップ３の段部の内面に接触するように
した。On this separator 5, a zinc alloy powder containing mercury-free aluminum, indium and bismuth,
A gel-like negative electrode mixture 6 composed of a thickener and an aqueous sodium hydroxide solution is placed, and the negative electrode mixture 6 is covered with the negative electrode cup 3 inside the opening edge of the positive electrode can 1 and 66 nylon 610.
Insert through a nylon ring-shaped J-shaped gasket 20 made by applying nylon and swage (horizontal tightening)
Then, they were caulked and sealed to produce an alkaline battery. In this case, the tip of the gasket 20 having a J-shaped cross section inside the negative electrode cup 3 was brought into contact with the inner surface of the step portion of the negative electrode cup 3.
【００３２】〔比較例１〕比較例１は、図７に示す如く
従来例図４の構成でＳＲ６２６ＳＷ電池を構成すると共
にガスケットとして実施例１と同様の断面Ｊ字状ガスケ
ット２０を使用した。即ち負極カップ３の内面の前面に
０．１５μｍ厚のスズ被覆層３０をスズの無電解メッキ
により形成し、正極缶１の開口端を断面Ｊ字状ガスケッ
ト２０を介して負極カップ３によって封止した。この図
７において図３、図４に対応する部分には同一符号を付
して重複説明は省略する。[Comparative Example 1] In Comparative Example 1, as shown in FIG. 7, a SR626SW battery was constructed with a conventional example shown in FIG. 4, and the same J-shaped gasket 20 as in Example 1 was used as a gasket. That is, a 0.15 μm thick tin coating layer 30 is formed on the inner surface of the negative electrode cup 3 by electroless plating of tin, and the opening end of the positive electrode can 1 is sealed by the negative electrode cup 3 via a J-shaped cross section gasket 20. did. In FIG. 7, parts corresponding to those in FIGS. 3 and 4 are designated by the same reference numerals, and duplicate description will be omitted.
【００３３】〔比較例２〕比較例２は図５に示す如き従
来例の構成でＳＲ６２６ＳＷ電池を構成した。即ち負極
カップ３の内面のＵ字状折り返し部１３の折り返し底部
１３ａを含まない内面領域にスズの無電解メッキにて、
０．１５μｍ厚のスズ被覆層３４を形成し、正極缶１の
開口端を断面Ｌ字状のガスケット２を介して負極カップ
３によって封止した。[Comparative Example 2] In Comparative Example 2, an SR626SW battery was constructed with a conventional configuration as shown in FIG. That is, by electroless plating of tin on the inner surface region of the negative electrode cup 3 not including the folded back portion 13a of the U-shaped folded portion 13,
A tin coating layer 34 having a thickness of 0.15 μm was formed, and the open end of the positive electrode can 1 was sealed with the negative electrode cup 3 via the gasket 2 having an L-shaped cross section.
【００３４】〔比較例３〕比較例３は、図４に示す如き
従来例の構成でＳＲ６２６ＳＷ電池を構成した。即ち、
負極カップ３の内面の全面にスズの無電解メッキにて、
０．１５μｍ厚のスズ被覆層３０を形成し、正極缶１の
開口端を断面Ｌ字状のガスケット２を介して負極カップ
３によって封止した。[Comparative Example 3] In Comparative Example 3, an SR626SW battery was constructed with the configuration of the conventional example as shown in FIG. That is,
By electroless plating of tin on the entire inner surface of the negative electrode cup 3,
A tin coating layer 30 having a thickness of 0.15 μm was formed, and the open end of the positive electrode can 1 was sealed with a negative electrode cup 3 via a gasket 2 having an L-shaped cross section.
【００３５】〔比較例４〕比較例４は、図６に示す如く
従来例図３の構成でＳＲ６２６ＳＷを構成すると共にガ
スケットとして実施例１と同様の断面Ｊ字状ガスケット
２０を使用した。即ち、負極カップ３の内面にはスズ被
覆層を設けず、正極缶１の開口端を断面Ｊ字状ガスケッ
ト２０を介して負極カップ３によって封止した。この図
６において、図３に対応する部分には同一符号を付して
重複説明は省略する。[Comparative Example 4] In Comparative Example 4, as shown in FIG. 6, SR626SW was constructed in the conventional example shown in FIG. 3, and the same J-shaped cross section gasket 20 as in Example 1 was used as the gasket. That is, the tin coating layer was not provided on the inner surface of the negative electrode cup 3, and the open end of the positive electrode can 1 was sealed by the negative electrode cup 3 via the J-shaped cross section gasket 20. In FIG. 6, parts corresponding to those in FIG. 3 are designated by the same reference numerals, and duplicate description will be omitted.
【００３６】〔比較例５〕比較例５は、図３に示す如き
従来例の構成でＳＲ６２６ＳＷ電池を構成した。即ち、
負極カップ３の内面にはスズ被覆層を設けず、正極缶１
の開口端を断面Ｌ字状ガスケット２を介して負極カップ
３によって封止した。[Comparative Example 5] In Comparative Example 5, an SR626SW battery was constructed with the configuration of the conventional example as shown in FIG. That is,
The tin coating layer is not provided on the inner surface of the negative electrode cup 3, and the positive electrode can 1
The open end of was sealed with a negative electrode cup 3 through an L-shaped cross section gasket 2.
【００３７】上述した実施例１、比較例１〜５の電池を
それぞれ１１０個づつ作製した。之等１００個ずつの電
池を、温度４５℃、相対湿度９３％の過酷環境下で保存
し、１４０日及び１６０日後の漏液発生率についての測
定結果を表１に示す。また、之等１０個づつの電池を温
度６０℃、相対湿度０％の環境で１００日間保存し、３
０ｋΩで定抵抗放電させ、１．４Ｖを終止電圧とした時
の放電容量〔ｍＡｈ〕を表１に示す。このいずれの電池
も初期放電容量は２８ｍＡｈ前後であった。110 batteries of each of the above-described Example 1 and Comparative Examples 1 to 5 were produced. Each 100 batteries were stored under a severe environment of a temperature of 45 ° C. and a relative humidity of 93%, and the measurement results of the liquid leakage occurrence rate after 140 days and 160 days are shown in Table 1. Also, store 10 batteries each for 100 days in an environment with a temperature of 60 ° C and relative humidity of 0%.
Table 1 shows the discharge capacity [mAh] when constant resistance discharge was performed at 0 kΩ and the final voltage was 1.4 V. The initial discharge capacity of each of these batteries was around 28 mAh.
【００３８】[0038]
【表１】 [Table 1]
【００３９】この表１より比較例４と比較例５とを比較
するに断面Ｊ字状ガスケット２０を用いることで耐漏液
特性を向上できることがわかる。これは断面Ｊ字状ガス
ケット２０の先端を負極カップ３の段部内面に接触させ
ることにより内部アルカリ電解液の移動を抑制したと考
えられる。It can be seen from Table 1 that the liquid leakage resistance can be improved by using the J-shaped cross section gasket 20 for comparing Comparative Example 4 and Comparative Example 5. It is considered that this is because the movement of the internal alkaline electrolyte was suppressed by bringing the tip of the J-shaped gasket 20 in contact with the inner surface of the step portion of the negative electrode cup 3.
【００４０】また実施例１、比較例１〜３と比較例４と
を比較するに負極カップ３の内面にスズ被覆層３０，３
４を設けることが保存後の容量を維持していることがわ
かる。これは負極カップ３の内面に銅よりも水素過電圧
の高い被覆層３０，３４を設けることで、負極活物質で
ある亜鉛が負極カップ３の集電体（銅）層３３と接する
ことにより発生する水素ガス（Ｈ2 ）を抑制し、亜鉛の
腐食を抑制したと考えられる。To compare Example 1, Comparative Examples 1 to 3 and Comparative Example 4, the tin coating layers 30 and 3 were formed on the inner surface of the negative electrode cup 3.
It can be seen that the provision of 4 maintains the capacity after storage. This occurs when the negative electrode active material zinc is in contact with the current collector (copper) layer 33 of the negative electrode cup 3 by providing the coating layers 30 and 34 having a hydrogen overvoltage higher than that of copper on the inner surface of the negative electrode cup 3. It is considered that the hydrogen gas (H 2 ) was suppressed and the corrosion of zinc was suppressed.
【００４１】実施例１と比較例１及び比較例２と比較例
３を比較するに負極カップ３の内面のＵ字状折り返し部
１３の折り返し底部１３ａ及び折り返し部１３ｂを除く
内面領域にのみスズ被覆層３４を設けたことで耐漏液特
性を向上できることがわかる。これは負極カップ３のＵ
字状折り返し部１３の折り返し底部１３ａにスズ被覆層
を設けないことで、アルカリ電解液のクリープ現象を抑
制したと考えられる。In comparing Example 1 with Comparative Example 1 and Comparative Example 2 with Comparative Example 3, tin coating is applied only to the inner surface region of the U-shaped folded portion 13 of the negative electrode cup 3 excluding the folded bottom portion 13a and the folded portion 13b. It can be seen that the liquid leakage resistance can be improved by providing the layer 34. This is U of the negative electrode cup 3.
It is considered that the creep phenomenon of the alkaline electrolyte was suppressed by not providing the tin coating layer on the folded bottom portion 13a of the character-shaped folded portion 13.
【００４２】実施例１と比較例２と比較するに断面Ｊ字
状ガスケット２０を用いて、この断面Ｊ字状ガスケット
２０の負極カップ３内の先端を負極カップ３の段部内面
に接触するようにしたことで保存後の容量を維持できる
ことがわかる。これはスズ被覆層３４を設ける際の精度
に多少のばらつきがあっても、この断面Ｊ字状ガスケッ
ト２０の先端と負極カップ３の内面とが接触しているこ
とにより、アルカリ電解液の移動が阻止され、負極カッ
プ３の集電体（銅）層３３の非被覆面での負極活物質で
ある亜鉛の腐食反応が進行しなかったものと考えられ
る。In comparison with Example 1 and Comparative Example 2, a J-shaped gasket 20 in cross section was used, and the tip of the gasket 20 in J-shaped cross section was contacted with the inner surface of the stepped portion of the negative electrode cup 3. It can be seen that the storage capacity can be maintained after the storage. This is because even if there is some variation in accuracy when the tin coating layer 34 is provided, the movement of the alkaline electrolyte is prevented because the tip of the gasket 20 having a J-shaped cross section is in contact with the inner surface of the negative electrode cup 3. It is considered that the corrosion reaction of zinc, which is the negative electrode active material, on the non-coated surface of the current collector (copper) layer 33 of the negative electrode cup 3 did not proceed due to the inhibition.
【００４３】本例によれば、負極カップ３の内面にＵ字
状折り返し部１３の折り返し底部１３ａ及び外部折り返
し部１３ｂを除く内面領域にスズ被覆層３４を設けたの
で、負極活物質である亜鉛が負極カップ３の集電体
（銅）層３３と接することにより発生する水素ガス（Ｈ
2 ）を抑制し、この亜鉛の腐食を抑制できると共にアル
カリ電解液のクリープ現象による耐漏液特性を向上でき
る。According to this example, since the tin coating layer 34 is provided on the inner surface of the negative electrode cup 3 except the folded bottom portion 13a of the U-shaped folded portion 13 and the outer folded portion 13b, the negative electrode active material zinc. Of hydrogen gas (H) generated by contact with the current collector (copper) layer 33 of the negative electrode cup 3.
2 ) can be suppressed, the corrosion of zinc can be suppressed, and the leakage resistance due to the creep phenomenon of the alkaline electrolyte can be improved.
【００４４】更に本例によれば、断面Ｊ字状ガスケット
２０の負極カップ３内の先端を負極カップ３の段部の内
面に接触するようにしたので耐漏液特性を向上させ且つ
この負極カップ３の内面にスズ被覆層３４を設ける際の
精度に多少のばらつきがあっても、この断面Ｊ字状ガス
ケット２０の先端と負極カップ３の内面とが接触してい
ることにより、アルカリ電解液の移動が阻止され、負極
カップ３の集電体（銅）層３３の負極活物質である亜鉛
の腐食反応が進行せず容量保存性の低下を改善できる。Further, according to this example, the tip of the gasket 20 having the J-shaped cross section inside the negative electrode cup 3 is brought into contact with the inner surface of the stepped portion of the negative electrode cup 3, so that the liquid leakage resistance is improved and the negative electrode cup 3 is improved. Even if there is some variation in accuracy when the tin coating layer 34 is provided on the inner surface of the negative electrode cup 3, the movement of the alkaline electrolyte is caused by the contact between the tip of the gasket 20 having the J-shaped cross section and the inner surface of the negative electrode cup 3. Is prevented, the corrosion reaction of zinc, which is the negative electrode active material of the current collector (copper) layer 33 of the negative electrode cup 3, does not proceed, and the deterioration of the capacity preservability can be improved.
【００４５】従って本例によれば、水銀を使用すること
なく良好なアルカリ電池を得ることができる。Therefore, according to this example, a good alkaline battery can be obtained without using mercury.
【００４６】尚、銅よりも水素過電圧の高い金属もしく
は合金としてはスズばかりでなくスズ、インジウム、ビ
スマスの１種以上の金属もしくは合金であっても良い。The metal or alloy having a higher hydrogen overvoltage than copper may be not only tin but also one or more metals or alloys of tin, indium and bismuth.
【００４７】またこの銅よりも水素過電圧の高い金属も
しくは合金の成膜方法は、無電解メッキ法ばかりでな
く、電解メッキ法、ＰＶＤ法、ＣＶＤ法であっても良
い。The method of forming a metal or alloy having a higher hydrogen overvoltage than copper is not limited to electroless plating, but may be electrolytic plating, PVD, or CVD.
【００４８】また、本発明は上述例に限ることなく本発
明の要旨を逸脱することなく、その他種々の構成が採り
得ることは勿論である。Further, the present invention is not limited to the above-mentioned examples, and it goes without saying that various other configurations can be adopted without departing from the gist of the present invention.
【００４９】[0049]
【発明の効果】本発明によれば、負極カップの内面にＵ
字状折り返し部の折り返し底部及び外部折り返し部を除
く内面領域に銅よりも水素過電圧の高い金属もしくは合
金の被膜を設けたので、負極活物質である亜鉛が負極カ
ップの集電体（銅）層と接することにより発生する水素
ガス（Ｈ2 ）を抑制し、この亜鉛の腐食を抑制できると
共にアルカリ電解液のクリープ現象による耐漏液特性を
向上できる。According to the present invention, U is formed on the inner surface of the negative electrode cup.
Since a metal or alloy film having a hydrogen overvoltage higher than that of copper is provided on the inner surface area of the folded back portion excluding the folded back portion and the outer folded portion, the negative electrode active material zinc is the current collector (copper) layer of the negative electrode cup. The hydrogen gas (H 2 ) generated by contact with the can be suppressed, the corrosion of zinc can be suppressed, and the liquid leakage resistance due to the creep phenomenon of the alkaline electrolyte can be improved.
【００５０】更に本発明によれば、ガスケットの負極カ
ップ内の先端を負極カップの段部の内面に接触するよう
にしたので耐漏液特性を向上させ且つこの負極カップの
内面に銅よりも水素過電圧の高い金属もしくは合金の被
膜を設ける際の精度に多少のばらつきがあっても、この
ガスケットの先端と負極カップの内面とが接触している
ことにより、アルカリ電解液の移動が阻止され、負極カ
ップの集電体（銅）層の負極活物質である亜鉛の腐食反
応が進行せず容量保存性の低下を改善できる。Further, according to the present invention, the tip of the gasket in the negative electrode cup is brought into contact with the inner surface of the step portion of the negative electrode cup, so that the liquid leakage resistance is improved and the hydrogen overvoltage is higher than that of copper on the inner surface of the negative electrode cup. Even if there is some variation in accuracy when forming a metal or alloy coating with high resistance, the movement of the alkaline electrolyte is blocked by the contact between the tip of this gasket and the inner surface of the negative electrode cup, and the negative electrode cup Since the corrosion reaction of zinc, which is the negative electrode active material of the current collector (copper) layer, does not proceed, it is possible to improve the decrease in capacity storage property.
【００５１】従って本発明によれば、水銀を使用するこ
となく良好なアルカリ電池を得ることができる。Therefore, according to the present invention, a good alkaline battery can be obtained without using mercury.
【図１】本発明アルカリ電池の実施の形態の例を示す概
略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an alkaline battery of the present invention.
【図２】本発明アルカリ電池の例の製造方法の一工程の
例の平面図である。FIG. 2 is a plan view of an example of one step of the manufacturing method of the alkaline battery of the present invention.
【図３】従来のアルカリ電池の例の概略断面図である。FIG. 3 is a schematic cross-sectional view of an example of a conventional alkaline battery.
【図４】従来のアルカリ電池の例の概略断面図である。FIG. 4 is a schematic cross-sectional view of an example of a conventional alkaline battery.
【図５】従来のアルカリ電池の例の概略断面図である。FIG. 5 is a schematic cross-sectional view of an example of a conventional alkaline battery.
【図６】従来のアルカリ電池の例の概略断面図である。FIG. 6 is a schematic cross-sectional view of an example of a conventional alkaline battery.
【図７】従来のアルカリ電池の例の概略断面図である。FIG. 7 is a schematic cross-sectional view of an example of a conventional alkaline battery.
１‥‥正極缶、３‥‥負極カップ、４‥‥正極合剤、５
‥‥セパレータ、６‥‥負極合剤、１３‥‥Ｕ字状折り
返し部、１３ａ‥‥折り返し底部、１３ｂ‥‥外周折り
返し部、２０‥‥Ｊ字状ガスケット、３１‥‥外表面
層、３２‥‥金属層、３３‥‥集電体層、３４‥‥スズ
被覆層1 ... positive electrode can, 3 ... negative electrode cup, 4 ... positive electrode mixture, 5
... Separator, 6 Negative electrode mixture, 13 ... U-shaped folded portion, 13a ... folded bottom portion, 13b ... outer peripheral folded portion, 20 ... J-shaped gasket, 31 ... outer surface layer, 32 ... Metal layer 33 Current collector layer 34 Tin coating layer
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H011 AA03 AA17 BB03 CC10 DD18 FF03 GG02 HH02 JJ02 JJ11 KK01 5H017 AA02 AS06 AS10 BB08 CC03 DD05 EE01 HH03 5H024 AA03 AA14 BB08 BB11 BB14 CC03 CC20 DD04 DD15 EE01 EE09 FF07 HH13 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 5H011 AA03 AA17 BB03 CC10 DD18 FF03 GG02 HH02 JJ02 JJ11 KK01 5H017 AA02 AS06 AS10 BB08 CC03 DD05 EE01 HH03 5H024 AA03 AA14 BB08 BB11 BB14 CC03 CC20 DD04 DD15 EE01 EE09 FF07 HH13
Claims (4)
物質とする正極合剤が配された正極缶と、亜鉛又は亜鉛
合金粉末を負極活物質とする負極合剤が配され、開口端
縁が断面Ｕ字状に外周面に沿って折り返し部及び折り返
し底部を有し、内面が銅より成る負極カップとをガスケ
ットを介して密封すると共に前記正極合剤と前記負極合
剤との間にセパレータを配し、アルカリ電解液を注入し
たアルカリ電池において、 前記負極カップの前記折り返し部及び折り返し底部を含
まない内面領域に銅よりも水素過電圧の高い金属もしく
は合金を成膜すると共に前記ガスケットの先端が前記負
極カップの内面に接触するようにしたことを特徴とする
アルカリ電池。1. A positive electrode can in which a positive electrode mixture containing silver oxide or manganese dioxide as a positive electrode active material is arranged, and a negative electrode mixture containing zinc or zinc alloy powder as a negative electrode active material are arranged, and an opening edge has a cross section. It has a U-shaped folded portion and a folded bottom portion along the outer peripheral surface, and the inner surface is sealed with a negative electrode cup made of copper through a gasket, and a separator is arranged between the positive electrode mixture and the negative electrode mixture. Then, in an alkaline battery injected with an alkaline electrolyte, a metal or alloy having a hydrogen overvoltage higher than that of copper is formed in the inner surface region of the negative electrode cup not including the folded back portion and the folded back bottom portion, and the tip of the gasket is the negative electrode. An alkaline battery characterized by being brought into contact with the inner surface of the cup.
の厚さを０．１０μｍ以上としたことを特徴とするアル
カリ電池。2. The alkaline battery according to claim 1, wherein the thickness of the metal or alloy having a higher hydrogen overvoltage than that of copper is 0.10 μm or more.
ズ、インジウム、ビスマスの１種類以上の金属もしくは
合金であることを特徴とするアルカリ電池。3. The alkaline battery according to claim 1, wherein the metal or alloy having a hydrogen overvoltage higher than that of copper is at least one metal or alloy of tin, indium, and bismuth.
方法は無電解メッキ法、電解メッキ法、ＰＶＤ法、ＣＶ
Ｄ法であることを特徴とするアルカリ電池。4. The alkaline battery according to claim 1, wherein a metal or alloy having a hydrogen overvoltage higher than that of copper is formed by electroless plating, electrolytic plating, PVD or CV.
An alkaline battery characterized by a D method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002070453A JP3997804B2 (en) | 2002-03-14 | 2002-03-14 | Alkaline battery |
| PCT/JP2003/002780 WO2003077338A1 (en) | 2002-03-14 | 2003-03-10 | Alkaline cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002070453A JP3997804B2 (en) | 2002-03-14 | 2002-03-14 | Alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003272636A true JP2003272636A (en) | 2003-09-26 |
| JP3997804B2 JP3997804B2 (en) | 2007-10-24 |
Family
ID=27800341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002070453A Expired - Lifetime JP3997804B2 (en) | 2002-03-14 | 2002-03-14 | Alkaline battery |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3997804B2 (en) |
| WO (1) | WO2003077338A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006172876A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Alkaline battery and its manufacturing method |
| JP2006172875A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Negative-electrode can, alkaline battery, and manufacturing method of them |
| JP2007080614A (en) * | 2005-09-13 | 2007-03-29 | Sony Corp | Alkaline battery |
| JP2008300084A (en) * | 2007-05-29 | 2008-12-11 | Seiko Instruments Inc | Electrode can plating method of flat form alkaline cell, anode can plating method of flat form alkaline cell, anode can plating device of flat form alkaline cell, anode can etching device of flat form alkaline cell, anode can surface reforming device of flat form alkaline cell, anode can cleaning device of flat form alkaline cell, and anode can drying device of flat form alkaline cell |
| JP2010015944A (en) * | 2008-07-07 | 2010-01-21 | Sony Corp | Alkaline cell |
| JP2012204154A (en) * | 2011-03-25 | 2012-10-22 | Seiko Instruments Inc | Button type alkaline battery anode can and button type alkaline battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0794154A (en) * | 1993-09-21 | 1995-04-07 | Hitachi Maxell Ltd | Alkaline button battery |
| JPH09147816A (en) * | 1995-11-17 | 1997-06-06 | Sony Corp | Alkaline button battery |
| JPH09161740A (en) * | 1995-12-12 | 1997-06-20 | Sony Corp | Alkaline button battery |
| JP2001307739A (en) * | 2000-04-18 | 2001-11-02 | Sony Corp | Alkaline battery |
-
2002
- 2002-03-14 JP JP2002070453A patent/JP3997804B2/en not_active Expired - Lifetime
-
2003
- 2003-03-10 WO PCT/JP2003/002780 patent/WO2003077338A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006172876A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Alkaline battery and its manufacturing method |
| JP2006172875A (en) * | 2004-12-15 | 2006-06-29 | Sii Micro Parts Ltd | Negative-electrode can, alkaline battery, and manufacturing method of them |
| JP2007080614A (en) * | 2005-09-13 | 2007-03-29 | Sony Corp | Alkaline battery |
| JP2008300084A (en) * | 2007-05-29 | 2008-12-11 | Seiko Instruments Inc | Electrode can plating method of flat form alkaline cell, anode can plating method of flat form alkaline cell, anode can plating device of flat form alkaline cell, anode can etching device of flat form alkaline cell, anode can surface reforming device of flat form alkaline cell, anode can cleaning device of flat form alkaline cell, and anode can drying device of flat form alkaline cell |
| JP2010015944A (en) * | 2008-07-07 | 2010-01-21 | Sony Corp | Alkaline cell |
| JP2012204154A (en) * | 2011-03-25 | 2012-10-22 | Seiko Instruments Inc | Button type alkaline battery anode can and button type alkaline battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3997804B2 (en) | 2007-10-24 |
| WO2003077338A1 (en) | 2003-09-18 |
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