JP2002198014A - Alkaline cell - Google Patents
Alkaline cellInfo
- Publication number
- JP2002198014A JP2002198014A JP2000392872A JP2000392872A JP2002198014A JP 2002198014 A JP2002198014 A JP 2002198014A JP 2000392872 A JP2000392872 A JP 2000392872A JP 2000392872 A JP2000392872 A JP 2000392872A JP 2002198014 A JP2002198014 A JP 2002198014A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- copper
- positive electrode
- folded
- cup
- 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
Classifications
-
- Y02E60/12—
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電子腕時計、電子卓
上計算機等の小型電子機器に使用されるコイン形及びボ
タン形のアルカリ電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to coin-type and button-type alkaline batteries used in small electronic devices such as electronic watches and electronic desk calculators.
【０００２】[0002]
【従来の技術】一般に、電子腕時計、電子卓上計算機等
の小型電子機器に使用されているコイン形及びボタン形
のアルカリ電池では、負極合剤に亜鉛又は亜鉛合金粉末
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、亜鉛又は亜鉛合金粉末から発生する水素ガスＨ2 及
び亜鉛又は亜鉛合金粉末が集電体（負極カップ）とアル
カリ電解液を介して接触することにより集電体（負極カ
ップ）から発生する水素ガスＨ2 を抑制するようにして
いる。2. Description of the Related Art In general, coin-type and button-type alkaline batteries used in small electronic devices such as electronic wristwatches and electronic desk calculators are manufactured by merging mercury into amalgamated zinc or zinc alloy powder in a negative electrode mixture. By using zinc, the hydrogen gas H 2 generated from the zinc or zinc alloy powder and the zinc or zinc alloy powder come into contact with the current collector (negative electrode cup) via an alkaline electrolyte to form a current collector (negative electrode cup). so as to suppress hydrogen gas H 2 generated from).
【０００３】この水素ガスＨ2 を発生する反応は亜鉛又
は亜鉛合金粉末がアルカリ電解液に溶解する反応であ
り、酸化されて水酸化亜鉛又は酸化亜鉛に変化するとき
の反応である。The reaction for generating hydrogen gas H 2 is a reaction in which zinc or a zinc alloy powder is dissolved in an alkaline electrolyte, and is a reaction when oxidized to change to zinc hydroxide or zinc oxide.
【０００４】従って、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り、容量保存性の低下、内圧
の上昇による耐漏液性の低下、更にこのアルカリ電池の
膨れや破裂を抑制する効果がある。[0004] Therefore, the use of zinc aromatized with mercury has the effect of lowering the capacity preservation, lowering the liquid leakage resistance due to an increase in internal pressure, and suppressing the swelling and rupture of the alkaline battery. .
【０００５】[0005]
【発明が解決しようとする課題】然し、近年環境問題の
観点からこのコイン形及びボタン形のアルカリ電池でも
水銀の使用をできるだけ避ける方向にあり、水銀を不要
にするための多くの研究がなされている。However, from the viewpoint of environmental problems, the use of mercury in coin-type and button-type alkaline batteries has been in the direction of minimizing the use of mercury in recent years, and many studies have been made to eliminate the use of mercury. I have.
【０００６】このアルカリ電解液中の亜鉛又は亜鉛粉末
から発生する水素ガスＨ2 の発生を抑える方法として
は、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ガスＨ2 の発生を抑え
るインヒビターを添加する方法が知られている。As a method for suppressing the generation of hydrogen gas H 2 generated from zinc or zinc powder in the alkaline electrolyte, a method of adding a metal having a high hydrogen overvoltage as an alloy to the zinc powder, a method of adding hydrogen gas to the alkaline electrolyte, There is known a method of adding an inhibitor for suppressing the generation of H 2 .
【０００７】然しながら、之等の知られている方法で
は、亜鉛又は亜鉛合金粉末が集電体（負極カップ）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Ｈ 2 を完全に抑えることができない。この水素ガス
Ｈ2 の発生を抑えるために、この集電体（負極カップ）
の銅よりも水素過電圧の高い金属であるスズＳｎ、イン
ジウムＩｎ、ビスマスＢｉや之等金属の１種以上もしく
は合金をこの集電体（負極カップ）の銅面にメッキして
被覆する方法が提案されている。[0007] However, according to these known methods,
The zinc or zinc alloy powder is connected to the current collector (negative electrode cup)
Hydrogen generated by contact through Lucari electrolyte
Gas H TwoCannot be completely suppressed. This hydrogen gas
HTwoCurrent collector (negative electrode cup)
Sn, which is a metal having a higher hydrogen overvoltage than copper,
One or more metals such as indium, bismuth Bi, and the like
Is to plate the alloy on the copper surface of this current collector (negative cup)
Coating methods have been proposed.
【０００８】この集電体（負極カップ）に無電解メッキ
やバレルメッキ等で、スズＳｎ、インジウムＩｎ、ビス
マスＢｉや之等金属の１種以上もしくは合金を被覆する
と、この負極カップの折り返し部及び折り返し底部に
も、このスズＳｎ、インジウムＩｎ、ビスマスＢｉ等が
被着されることとなる。When the current collector (negative electrode cup) is coated with at least one of tin Sn, indium In, bismuth Bi, and the like or an alloy thereof by electroless plating or barrel plating, the folded portion of the negative electrode cup and The tin Sn, indium In, bismuth Bi, and the like are also applied to the folded bottom.
【０００９】また、この負極カップとして使用される３
層クラッド材の銅面にスズＳｎ、インジウムＩｎ、ビス
マスＢｉや之等金属の１種以上もしくは合金を全面に亘
って被覆した後に負極カップにプレス成形した場合にも
同様に、この負極カップの折り返し部及び折り返し底部
にもこのスズＳｎ、インジウムＩｎ、ビスマスＢｉ等が
被着される。[0009] In addition, 3 is used as the negative electrode cup.
Similarly, when the copper surface of the layer cladding material is coated with at least one or an alloy of tin Sn, indium In, bismuth Bi, or the like or an alloy over the entire surface and then press-formed into the negative electrode cup, the negative electrode cup is similarly folded. This tin Sn, indium In, bismuth Bi and the like are also applied to the portion and the folded bottom.
【００１０】この場合、亜鉛又は亜鉛合金粉末が負極カ
ップ（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Ｈ2 の発生の抑制には効果があ
るが、このスズＳｎ、インジウムＩｎ、ビスマスＢｉや
之等金属の１種以上もしくは合金はアルカリ電解液の這
い上がり（クリープ現象）が銅よりも大きく、このアル
カリ電池の耐漏液性を低下させる原因となる不都合があ
る。In this case, zinc or zinc alloy powder is effective in suppressing the generation of hydrogen gas H 2 generated by contact with the negative electrode cup (current collector) via the alkaline electrolyte. One or more metals or alloys of indium, indium, bismuth Bi, and the like have a problem that the alkaline electrolyte creeps up (creep phenomenon) more than copper, which causes a reduction in the leakage resistance of the alkaline battery.
【００１１】このため、この負極カップの折り返し部及
び折り返し底部を含まない内面領域のみに被覆を行い、
水素ガスＨ2 の発生とアルカリ電解液のクリープ現象と
を同時に抑制する技術が研究されてきた。For this reason, coating is performed only on the inner surface area of the negative electrode cup that does not include the folded portion and the folded bottom portion,
Techniques for simultaneously suppressing the generation of hydrogen gas H 2 and the creep phenomenon of the alkaline electrolyte have been studied.
【００１２】然しながら、部分的にメッキを施す方法を
量産化する場合、目的とする負極カップの折り返し部及
び折り返し底部を含まない内面領域のみに精度良くメッ
キを施す方法は困難であり、且つ洗浄時にメッキ液によ
りこの負極カップ（集電体）の銅面が酸化されることが
ある。However, when mass-producing the method of partially plating, it is difficult to accurately perform plating only on the inner surface area not including the folded portion and the folded bottom portion of the intended negative electrode cup. The plating solution may oxidize the copper surface of the negative electrode cup (current collector).
【００１３】水素ガスＨ2 の発生を抑制する効果のある
金属がこの負極カップの折り返し部及び折り返し底部に
存在しなくとも、この負極カップ（集電体）の母材の銅
面がメッキ液により酸化されることで、アルカリ電解液
のクリープ現象が大きくなり、耐漏液性を低下させる不
都合があった。[0013] Even if a metal having an effect of suppressing the generation of hydrogen gas H 2 is not present at the folded portion and the folded bottom portion of the negative electrode cup, the copper surface of the base material of the negative electrode cup (current collector) is exposed to the plating solution. Due to the oxidation, the creep phenomenon of the alkaline electrolyte increases, and there is a disadvantage that the leakage resistance is reduced.
【００１４】従って、水素ガスＨ2 の発生を抑制し、ア
ルカリ電解液のクリープ現象を抑制する技術は量産化が
困難であり、このため現在まで、水銀を含んでいない、
このコイン形及びボタン形のアルカリ電池は市販されて
いない。Therefore, it is difficult to mass-produce the technology for suppressing the generation of hydrogen gas H 2 and suppressing the creep phenomenon of the alkaline electrolyte.
These coin-shaped and button-shaped alkaline batteries are not commercially available.
【００１５】本発明は、斯る点に鑑み、水銀を含んでい
ないコイン形及びボタン形のアルカリ電池を提案せんと
するものである。In view of the above, the present invention proposes coin-type and button-type alkaline batteries which do not contain mercury.
【００１６】[0016]
【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、外周に折り返し部及び折
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であって、この負極カップの折り返
し部及び折り返し底部を含まない内面領域に乾式成膜法
により銅よりも水素過電圧の高い金属もしくは合金を成
膜したものである。According to the present invention, there is provided an alkaline battery comprising:
A positive electrode can and a negative electrode mixture containing zinc or zinc alloy powder as a negative electrode active material are disposed, and a folded portion and a folded bottom are provided on the outer periphery, and a positive electrode mixture containing silver oxide or manganese dioxide as a positive electrode active material is provided. A negative electrode cup whose inner surface is made of copper is sealed via a gasket, a separator is arranged between the positive electrode mixture and the negative electrode mixture, and an alkaline battery in which an alkaline electrolyte is injected, A metal or alloy having a higher hydrogen overvoltage than copper is formed by a dry film forming method on an inner surface area not including the turned-back portion and the turned-back bottom.
【００１７】本発明によれば、負極カップの内面領域に
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、水銀を使用することなく、水素ガスＨ2 の発生を
抑制できると共にこの負極カップの折り返し部及び折り
返し底部に銅よりも水素過電圧の高い金属もしくは合金
を成膜しないので、アルカリ電解液の這い上がり（クリ
ープ現象）が増大せず耐漏液性が低下することがなく、
また、この銅よりも水素過電圧の高い金属もしくは合金
を乾式成膜法により成膜するようにしたので、この負極
カップの折り返し部及び折り返し底部の銅面が酸化され
ることがなく、アルカリ電解液のクリープ現象による耐
漏液性を低下することがない。According to the present invention, since a metal or alloy having a higher hydrogen overvoltage than copper is formed on the inner surface area of the negative electrode cup, the generation of hydrogen gas H 2 can be suppressed without using mercury and the negative electrode can be formed. Since the metal or alloy having a higher hydrogen overvoltage than copper is not formed on the folded portion and the folded bottom portion of the cup, the creeping of the alkaline electrolyte (creep phenomenon) does not increase, and the leakage resistance does not decrease.
In addition, since a metal or an alloy having a higher hydrogen overvoltage than copper is formed by a dry film forming method, the copper surface of the folded portion and the folded bottom portion of the negative electrode cup is not oxidized, and the alkaline electrolytic solution is used. The leak resistance due to the creep phenomenon does not decrease.
【００１８】[0018]
【発明の実施の形態】以下、図面を参照して本発明アル
カリ電池の実施の形態例につき説明しよう。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the alkaline battery of the present invention will be described below with reference to the drawings.
【００１９】図１において、１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を示し、本例にお
いてはこの正極合剤１をコイン状のペレットに成形す
る。このコイン状のペレットの正極合剤１をステンレス
スチール板にニッケルメッキを施した正極端子及び正極
集電体を兼ねた正極缶２に配する。In FIG. 1, reference numeral 1 denotes a positive electrode mixture using silver oxide or manganese dioxide as a positive electrode active material. In this embodiment, the positive electrode mixture 1 is formed into a coin-shaped pellet. The coin-shaped pellet of the positive electrode mixture 1 is placed in a positive electrode terminal 2 formed by nickel-plating a stainless steel plate and a positive electrode can 2 also serving as a positive electrode current collector.
【００２０】また、３は亜鉛又は亜鉛合金粉末を負極活
物質とし、アルカリ電解液例えば水酸化ナトリウム水溶
液又は水酸化カリウム水溶液、増粘剤等からなり、水銀
を含まないジェル状の負極合剤を示し、この負極合剤３
を負極端子及び負極集電体を兼ねた負極カップ４に配す
る。Reference numeral 3 denotes a gel-like negative electrode mixture containing zinc or a zinc alloy powder as a negative electrode active material, comprising an alkaline electrolyte such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, a thickener, etc., and containing no mercury. This negative electrode mixture 3
In the negative electrode cup 4 which also serves as a negative electrode terminal and a negative electrode current collector.
【００２１】この正極合剤１と負極合剤３との間に不織
布、セロハン及びポリエチレンをグラフト重合した膜の
３層からなるセパレータ５を配する。このセパレータ５
にアルカリ電解液例えば水酸化ナトリウム水溶液又は水
酸化カリウム水溶液を含浸する如くする。Between the positive electrode mixture 1 and the negative electrode mixture 3, a separator 5 composed of three layers of a nonwoven fabric, a cellophane and a film obtained by graft-polymerizing polyethylene is disposed. This separator 5
Is impregnated with an alkaline electrolyte such as an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide.
【００２２】この正極缶２の内周で且つこのセパレータ
５の上部と負極カップ４の外周の折り返し部４ａ及び折
り返し底部４ｂと間にナイロン製のガスケット６を配し
て、この正極缶２と負極カップ４とをカシメて密封する
如くする。A gasket 6 made of nylon is arranged on the inner periphery of the positive electrode can 2 and between the upper part of the separator 5 and the folded part 4a and the folded bottom part 4b on the outer periphery of the negative electrode cup 4. The cup 4 is caulked and sealed.
【００２３】本例においては、負極カップ４としては、
図２に示す如くニッケル７、ステンレス８及び銅９の３
層クラッド材により形成し、外周に折り返し部４ａ及び
折り返し底部４ｂを形成する如くする。In this embodiment, the negative electrode cup 4 is
As shown in FIG. 2, three of nickel 7, stainless steel 8, and copper 9
It is made of a layer clad material, and a folded portion 4a and a folded bottom 4b are formed on the outer periphery.
【００２４】また、本例においては、この負極カップ４
のこの折り返し部４ａ及び折り返し底部４ｂを含まない
内面領域の銅９上に、銅よりも水素過電圧の高いスズＳ
ｎを乾式成膜法であるスパッタリング法により被覆し、
スズ被覆層１０を設けたものである。In this embodiment, the negative electrode cup 4
The tin S having a higher hydrogen overvoltage than copper is provided on the copper 9 in the inner surface area not including the turned-up portion 4a and the turned-down bottom 4b.
n is coated by a sputtering method which is a dry film forming method,
This is provided with a tin coating layer 10.
【００２５】本例によれば、表１の実施例１〜６に示す
如く、負極カップ４の内面に銅より水素過電圧の高いス
ズ被覆層１０を乾式成膜法のスパッタリング法により設
けたので、水素ガスＨ2 の発生を抑制することができる
と共に負極カップ４の折り返し部４ａ及び折り返し底部
４ｂに、ガスケット６のシール部分のアルカリ電解液の
這い上がりがスズ被覆層１０より小さい銅９面を残して
おり、且つ負極カップ４の折り返し部４ａ及び折り返し
底部４ｂの母材である銅９面の酸化が進行していないた
め耐漏液性を確保することができる。According to this example, as shown in Examples 1 to 6 in Table 1, the tin coating layer 10 having a higher hydrogen overvoltage than copper was provided on the inner surface of the negative electrode cup 4 by the sputtering method of the dry film forming method. The generation of hydrogen gas H 2 can be suppressed and the copper 9 surface, on which the alkaline electrolyte of the sealing portion of the gasket 6 rises smaller than the tin coating layer 10, is left at the folded portion 4 a and the folded bottom portion 4 b of the negative electrode cup 4. In addition, since the oxidation of the copper 9 surface, which is the base material of the folded portion 4a and the folded bottom portion 4b of the negative electrode cup 4, has not progressed, leakage resistance can be ensured.
【００２６】[0026]
【表１】 [Table 1]
【００２７】因みに、この表１の実施例１は負極カップ
４を以下のように形成したものである。まず、この負極
カップ４を形成しようとするニッケル７、ステンレス８
及び銅９から成る厚さ０．２ｍｍの３層クラッド材をプ
レス加工して図２に示す如きアルカリ電池例えばＳＲ６
２６ＳＷの負極カップ４を作製した。In Example 1 of Table 1, the negative electrode cup 4 was formed as follows. First, nickel 7 and stainless steel 8 for forming the negative electrode cup 4 are used.
And a 9 mm thick three-layer clad material made of copper 9 and pressed into an alkaline battery such as SR6 as shown in FIG.
A 26SW negative electrode cup 4 was produced.
【００２８】次に予め準備した図３に示す如く、負極カ
ップ４の折り返し部４ａ及び折り返し底部４ｂを覆い隠
すマスク１１にこの負極カップ４を設置し、スパッタリ
ングを行うことで内面領域に厚さ０．０１μｍのスズ被
覆層１０が設けられた負極カップ４を得た。この実施例
１では上述の負極カップ４を使用して、図１に示す如き
ボタン形のアルカリ電池を作製したものである。Next, as shown in FIG. 3 prepared in advance, the negative electrode cup 4 is set on a mask 11 that covers the folded portion 4a and the folded bottom portion 4b of the negative electrode cup 4, and sputtering is performed to reduce the thickness of the negative surface to the inner surface area. A negative electrode cup 4 provided with a 0.01 μm tin coating layer 10 was obtained. In the first embodiment, a button-shaped alkaline battery as shown in FIG. 1 was manufactured using the above-described negative electrode cup 4.
【００２９】即ち、図１に示す如き正極缶２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注入
し、次に酸化銀、二酸化マンガン、四フッ化ポリエチレ
ンからなる正極合剤１をコイン状に成形したペレットを
入れ、この正極合剤１に、このアルカリ電解液を吸収さ
せる如くする。That is, a 28% by weight aqueous solution of sodium hydroxide was poured into a positive electrode can 2 as shown in FIG. 1, and then a positive electrode mixture 1 comprising silver oxide, manganese dioxide and polyethylene tetrafluoride was added. A coin-shaped pellet is put therein, and the positive electrode mixture 1 is made to absorb the alkaline electrolyte.
【００３０】次に、この正極合剤１のペレット上に円形
に打ち抜いたグラフト重合したポリエチレンとセロハン
をラミネートしたフィルムと不織布との３層から成るセ
パレータ５を装填し、このセパレータ５上に６６ナイロ
ンに６１０ナイロンを塗布したガスケット６を装填す
る。Next, a separator 5 composed of three layers of a film obtained by laminating a graft-polymerized polyethylene and cellophane laminated on a pellet of the positive electrode mixture 1 and a nonwoven fabric was loaded on the pellet, and 66 nylon was placed on the separator 5. Is charged with a gasket 6 coated with 610 nylon.
【００３１】次にこのセパレータ５の不織布に、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
して含浸する。このセパレータ５の不織布上に、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なるジ
ェル状の負極合剤３を載置し、この負極合剤３上に負極
カップ４を装填する。次に、スェージ（横締め）し、正
極缶２をカシメて、ボタン形のアルカリ電池例えばＳＲ
６２６ＳＷを作製し、実施例１のアルカリ電池を得た。Next, the non-woven fabric of the separator 5 is impregnated with a 28% by weight aqueous solution of sodium hydroxide in an alkaline electrolyte. On the non-woven fabric of the separator 5, a gel-shaped negative electrode mixture 3 composed of a zinc alloy powder containing no mercury, aluminum, indium, and bismuth, a thickener, and an aqueous sodium hydroxide solution is placed. The negative electrode cup 4 is loaded thereon. Next, it is swaged (horizontally tightened), the positive electrode can 2 is swaged, and a button-type alkaline battery such as SR
626SW was produced, and the alkaline battery of Example 1 was obtained.
【００３２】また、この表１の実施例２の負極カップ４
は、実施例１と同様にしてスパッタリングを行い、折り
返し部４ａ及び折り返し底部４ｂを含まない内面領域に
厚さ０．１５μｍのスズ被覆層１０を設けたものであ
る。この実施例２のアルカリ電池は、この負極カップ４
を使用し、その他は実施例１と同様にして作製したボタ
ン形のアルカリ電池例えばＳＲ６２６ＳＷである。The negative electrode cup 4 of Example 2 in Table 1 was used.
Shows a case in which sputtering is performed in the same manner as in Example 1, and a tin coating layer 10 having a thickness of 0.15 μm is provided in an inner surface region not including the folded portion 4a and the folded bottom portion 4b. The alkaline battery of the second embodiment is similar to the negative electrode cup 4
And a button-shaped alkaline battery, for example, SR626SW, manufactured in the same manner as in Example 1.
【００３３】また、この表１の実施例３の負極カップ４
は、実施例１と同様にしてスパッタリングを行い、折り
返し部４ａ及び折り返し底部４ｂを含まない内面領域に
厚さ１．５０μｍのスズ被覆層１０を設けたものであ
る。この実施例３のアルカリ電池は、この負極カップ４
を使用し、その他は実施例１と同様にして作製したボタ
ン形のアルカリ電池例えばＳＲ６２６ＳＷである。The negative electrode cup 4 of Example 3 in Table 1
In this example, sputtering was performed in the same manner as in Example 1, and a tin coating layer 10 having a thickness of 1.50 μm was provided in an inner surface region not including the folded portion 4a and the folded bottom portion 4b. The alkaline battery of the third embodiment is similar to the negative electrode cup 4
And a button-shaped alkaline battery, for example, SR626SW, manufactured in the same manner as in Example 1.
【００３４】また、この表１の実施例４の負極カップ４
は、実施例１と同様にマスク１１に負極カップ４を設置
し、真空蒸着を行うことで内面領域に厚さ０．０１μｍ
のスズ被覆層１０を設けたものである。この実施例４の
アルカリ電池は、この負極カップ４を使用し、その他は
実施例１と同様にして作製したボタン形のアルカリ電池
例えばＳＲ６２６ＳＷである。The negative electrode cup 4 of Example 4 in Table 1 was used.
In the same manner as in Example 1, the negative electrode cup 4 was placed on the mask 11 and vacuum evaporation was performed to make the inner surface region have a thickness of 0.01 μm.
Is provided with a tin coating layer 10. The alkaline battery of the fourth embodiment is a button-shaped alkaline battery, for example, SR626SW, manufactured using the negative electrode cup 4 and in the same manner as in the first embodiment.
【００３５】また、この表１の実施例５の負極カップ４
は、実施例１と同様にマスク１１に負極カップ４を設置
し、乾式成膜法である真空蒸着を行うことで内面領域に
厚さ０．１５μｍのスズ被覆層１０を設けたものであ
る。この実施例５のアルカリ電池は、この負極カップ４
を使用し、その他は実施例１と同様にして作製したボタ
ン形のアルカリ電池例えばＳＲ６２６ＳＷである。The negative electrode cup 4 of Example 5 in Table 1 was used.
In the same manner as in Example 1, the negative electrode cup 4 was placed on the mask 11 and vacuum deposition was performed as a dry film forming method to provide a tin coating layer 10 having a thickness of 0.15 μm on the inner surface region. The alkaline battery of the fifth embodiment is similar to the negative electrode cup 4
And a button-shaped alkaline battery, for example, SR626SW, manufactured in the same manner as in Example 1.
【００３６】また、この表１の実施例６の負極カップ４
は、実施例１と同様にマスク１１に負極カップ４を設置
し、真空蒸着を行うことで内面領域に厚さ１．５０μｍ
のスズ被覆層１０を設けたものである。この実施例６の
アルカリ電池は、この負極カップ４を使用し、その他は
実施例１と同様にして作製したボタン形のアルカリ電池
例えばＳＲ６２６ＳＷである。The negative electrode cup 4 of Example 6 in Table 1 was used.
In the same manner as in Example 1, the negative electrode cup 4 was set on the mask 11 and vacuum deposition was performed to make the inner surface region have a thickness of 1.50 μm.
Is provided with a tin coating layer 10. The alkaline battery of the sixth embodiment is a button-type alkaline battery, for example, SR626SW, which is manufactured in the same manner as in the first embodiment except that the negative electrode cup 4 is used.
【００３７】また、この表１の比較例１は、負極カップ
４の折り返し部４ａ及び折り返し底部４ｂを含まない内
面領域に厚さ０．１５μｍの無電解スズメッキを施し、
その他は実施例１と同様にして作製したボタン形のアル
カリ電池例えばＳＲ６２６ＳＷである。In Comparative Example 1 of Table 1, electroless tin plating having a thickness of 0.15 μm was applied to the inner surface area of the negative electrode cup 4 which did not include the folded portion 4a and the folded bottom portion 4b.
The other components are button-type alkaline batteries manufactured in the same manner as in Example 1, for example, SR626SW.
【００３８】また、この表１の比較例２は、負極カップ
４にスズ被覆層を設けない他は実施例１と同様に作製し
たアルカリ電池例えばＳＲ６２６ＳＷである。Comparative Example 2 in Table 1 is an alkaline battery, for example, SR626SW, produced in the same manner as in Example 1 except that the negative electrode cup 4 was not provided with a tin coating layer.
【００３９】上述の実施例１〜６、比較例１、２のそれ
ぞれのアルカリ電池を２００個ずつ用意し、温度４５
℃、相対湿度９３％の環境下で保存し、１００日後、１
２０日後、１４０日後、１６０日後の漏液発生率を調べ
た。Each of the alkaline batteries of Examples 1 to 6 and Comparative Examples 1 and 2 was prepared by 200 pieces at a temperature of 45 ° C.
At 100 ° C and a relative humidity of 93%.
After 20 days, 140 days, and 160 days, the rate of liquid leakage was examined.
【００４０】この結果は、表１に示す如く、乾式成膜法
により折り返し部４ａ及び折り返し底部４ｂを含まない
内面領域にスズ被覆層１０が設けられている負極カップ
４を使用した実施例１〜６のアルカリ電池はいずれも、
スズ被覆層１０を無電解メッキ法にて設けた負極カップ
４を使用した比較例１のアルカリ電池に比較して温度４
５℃、相対湿度９３％の環境下で保存したときの漏液発
生率が減少している。The results are shown in Table 1 as shown in Examples 1 to 4 in which the negative electrode cup 4 in which the tin coating layer 10 was provided in the inner surface region not including the folded portion 4a and the folded bottom portion 4b by the dry film forming method was used. All 6 alkaline batteries
Compared with the alkaline battery of Comparative Example 1 using the negative electrode cup 4 provided with the tin coating layer 10 by the electroless plating method, the temperature was 4
The rate of occurrence of liquid leakage when stored in an environment at 5 ° C. and a relative humidity of 93% is reduced.
【００４１】この理由は実施例１〜６のアルカリ電池の
負極カップ４の折り返し部４ａ及び折り返し底部４ｂに
酸化膜層が形成されていないので、アルカリ電解液の這
い上がり（クリープ現象）が増大せず耐漏液特性が向上
したものと思われる。The reason for this is that since the oxide film layer is not formed on the folded portion 4a and the folded bottom portion 4b of the negative electrode cup 4 of the alkaline batteries of Examples 1 to 6, creeping of the alkaline electrolyte (creep phenomenon) is increased. It is thought that the liquid leakage resistance was improved.
【００４２】また、この実施例１〜６、比較例１、２の
それぞれのアルカリ電池を５個ずつ用意し、３０ｋΩの
負荷で終止電圧１．４Ｖまで放電し放電容量を調査し、
初度の放電容量を得た。次に、６０℃の環境下で保存
し、１００日後の放電容量を得た。Further, five alkaline batteries of each of Examples 1 to 6 and Comparative Examples 1 and 2 were prepared and discharged to a cutoff voltage of 1.4 V with a load of 30 kΩ, and the discharge capacity was examined.
The first discharge capacity was obtained. Next, the battery was stored in an environment of 60 ° C., and a discharge capacity after 100 days was obtained.
【００４３】この結果は、表１に示す如く、乾式成膜法
により折り返し部４ａ及び折り返し底部４ｂを含まない
内面領域にスズ被覆層１０が設けられた負極カップ４を
使用した実施例１〜６のアルカリ電池はいずれも、スズ
被覆層１０を設けない負極カップを使用した比較例２の
アルカリ電池に比較して６０℃の環境下で１００日保存
したときの放電容量が向上している。また比較例１の無
電解メッキ法にて折り返し部４ａ及び折り返し底部４ｂ
を含まない内面領域にスズ被覆層１０を設けたアルカリ
電池に比較して、実施例１及び４のスパッタリング法も
しくは真空蒸着法により被覆層１０の厚さを０．０１μ
ｍにした場合でも６０℃の環境下で１００日後の放電容
量は同等以上である。このことから乾式成膜法による負
極カップ４のスズ被覆層１０は０．０１μｍ以上であれ
ば良い。The results are shown in Tables 1 to 6 in Examples 1 to 6 using the negative electrode cups 4 provided with the tin coating layer 10 in the inner surface area not including the folded portion 4a and the folded bottom portion 4b by the dry film forming method. Each of the alkaline batteries has an improved discharge capacity when stored for 100 days in an environment of 60 ° C. as compared with the alkaline battery of Comparative Example 2 using the negative electrode cup without the tin coating layer 10. The folded portion 4a and the folded bottom portion 4b were formed by the electroless plating method of Comparative Example 1.
The thickness of the coating layer 10 was set to 0.01 μm by the sputtering method or the vacuum evaporation method of Examples 1 and 4 as compared with the alkaline battery in which the tin coating layer 10 was provided in the inner surface region not containing
The discharge capacity after 100 days in an environment of 60 ° C. is equal to or greater than that of the case of m. From this, it is sufficient that the tin coating layer 10 of the negative electrode cup 4 by the dry film forming method is 0.01 μm or more.
【００４４】以上述べた如く、本例によれば負極カップ
４の内面に乾式成膜法により銅よりも水素過電圧の高い
スズ被覆層１０を設けたので、水素ガスＨ2 の発生を抑
制することができると共にこの負極カップ４の折り返し
部４ａ及び折り返し底部４ｂに、ガスケットのシール部
分のアルカリ電解液の這い上がりがスズ被覆層より小さ
い銅９面を残し、且つ負極カップ４の折り返し部４ａ及
び折り返し底部４ｂに母材である銅面に酸化被膜層を形
成させないでいるため、耐漏液性を確保することができ
る。As described above, according to the present embodiment, since the tin coating layer 10 having a higher hydrogen overvoltage than copper is provided on the inner surface of the negative electrode cup 4 by the dry film forming method, the generation of hydrogen gas H 2 is suppressed. At the folded portion 4a and the folded bottom portion 4b of the negative electrode cup 4, a copper 9 surface on which the rising of the alkaline electrolyte in the sealing portion of the gasket is smaller than the tin coating layer is left, and the folded portion 4a and the folded portion of the negative electrode cup 4 are formed. Since the oxide film layer is not formed on the copper surface serving as the base material on the bottom portion 4b, the liquid leakage resistance can be ensured.
【００４５】即ち、本例によれば、負極カップ４の折り
返し部４ａ及び折り返し底部４ｂを含まない内面領域に
乾式成膜法によりスズ被覆層１０を設けることで、水銀
を使用しなくとも水素ガスＨ2 の発生を抑制し、負極カ
ップ４の折り返し部４ａ及び折り返し底部４ｂに母材で
ある銅の酸化被膜層が形成されないためアルカリ電池の
漏液発生及び膨れや破裂を抑制することができる。That is, according to the present embodiment, the tin coating layer 10 is provided on the inner surface area of the negative electrode cup 4 that does not include the folded portion 4a and the folded bottom portion 4b by the dry film forming method, so that hydrogen gas can be used without using mercury. The generation of H 2 is suppressed, and the oxide layer of copper, which is the base material, is not formed on the folded portion 4a and the folded bottom portion 4b of the negative electrode cup 4, so that the occurrence of liquid leakage, swelling, and rupture of the alkaline battery can be suppressed.
【００４６】尚、上述例では乾式成膜法としてスパッタ
リング法、真空蒸着を使用した例につき述べたが、この
乾式成膜法としては、イオンプレーティング等のその他
のＰＶＤ（Physical vapor deposition)法や、熱、プラ
ズマ、光等のＣＶＤ（Chemical vapor deposition)が使
用できる。In the above-described example, an example in which a sputtering method and a vacuum deposition method are used as the dry film forming method has been described. However, as the dry film forming method, other PVD (Physical vapor deposition) methods such as ion plating and the like can be used. , Heat, plasma, light, etc., CVD (Chemical vapor deposition) can be used.
【００４７】また上述例では銅よりも水素過電圧の高い
金属としてスズＳｎを被覆したがこの代りに、スズＳ
ｎ、インジウムＩｎ、ビスマスＢｉの１種以上の金属も
しくは合金であっても良い。In the above example, tin Sn was coated as a metal having a higher hydrogen overvoltage than copper.
One or more metals or alloys of n, indium In, and bismuth Bi may be used.
【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-described example, 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、水銀を使用することなく、水素ガスＨ2 の発生
を抑制できると共にこの負極カップの折り返し部及び折
り返し底部に銅よりも水素過電圧の高い金属もしくは合
金を成膜しないので、アルカリ電解液の這い上がり（ク
リープ現象）が増大せず耐漏液性が低下することがな
く、また、この銅よりも水素過電圧の高い金属もしくは
合金を乾式成膜法により成膜するようにしたので、この
負極カップの折り返し部及び折り返し底部の銅面が酸化
されることがなく、アルカリ電解液のクリープ現象によ
る耐漏液性を低下することがない。According to the present invention, since a metal or an alloy having a higher hydrogen overvoltage than copper is formed in the inner surface region of the negative electrode cup, the generation of hydrogen gas H 2 can be suppressed without using mercury. Since a metal or an alloy having a higher hydrogen overvoltage than copper is not formed on the folded portion and the folded bottom portion of the negative electrode cup, creeping of the alkaline electrolyte (creep phenomenon) does not increase, and the leakage resistance does not decrease. In addition, since a metal or an alloy having a higher hydrogen overvoltage than copper is formed by a dry film forming method, the copper surface of the folded portion and the folded bottom portion of the negative electrode cup is not oxidized, and the alkaline electrolytic solution is used. The leak resistance due to the creep phenomenon does not decrease.
【図１】本発明アルカリ電池の実施の形態の例を示す断
面図である。FIG. 1 is a sectional view showing an example of an embodiment of the alkaline battery of the present invention.
【図２】図１例の負極カップの例を示す断面図である。FIG. 2 is a sectional view showing an example of the negative electrode cup of FIG. 1;
【図３】本発明の要部の例の説明に供する線図である。FIG. 3 is a diagram for explaining an example of a main part of the present invention.
１‥‥正極合剤、２‥‥正極缶、３‥‥負極合剤、４‥
‥負極カップ、４ａ‥‥折り返し部、４ｂ‥‥折り返し
底部、５‥‥セパレータ、６‥‥ガスケット、７‥‥ニ
ッケル、８‥‥ステンレス、９‥‥銅、１０‥‥スズ被
覆層、１１‥‥マスク1 ‥‥ Positive electrode mixture, 2 ‥‥ Positive electrode can, 3 ‥‥ Negative electrode mixture, 4 ‥
{Negative electrode cup, 4a} folded part, 4b} folded bottom, 5} separator, 6} gasket, 7} nickel, 8} stainless steel, 9} copper, 10} tin coating layer, 11} ‥mask
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K029 AA02 AA26 BA02 BA10 BA15 BC00 BD00 CA01 CA03 CA05 EA01 5H011 AA17 CC06 CC10 DD17 DD18 FF03 KK01 5H017 AA02 AS06 BB00 BB08 CC01 EE01 HH03 5H024 AA03 AA14 BB00 CC03 DD02 EE01 FF07 FF36 HH13 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K029 AA02 AA26 BA02 BA10 BA15 BC00 BD00 CA01 CA03 CA05 EA01 5H011 AA17 CC06 CC10 DD17 DD18 FF03 KK01 5H017 AA02 AS06 BB00 BB08 CC01 EE01 HH03 5H024 AA03 FF00
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、外周に折
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であって、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
面領域に乾式成膜法により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 using silver oxide or manganese dioxide as a positive electrode active material is disposed, and a negative electrode mixture using zinc or zinc alloy powder as a negative electrode active material is disposed. An alkaline battery having a bottom portion, a separator between the positive electrode mixture and the negative electrode mixture while sealing a negative electrode cup whose inner surface is made of copper via a gasket, and injecting an alkaline electrolyte. An alkaline battery, wherein a metal or an alloy having a higher hydrogen overvoltage than copper is formed by a dry film forming method on an inner surface area of the negative electrode cup that does not include the folded portion and the folded bottom portion.
プレーティング等によるＰＶＤ法もしくは熱、プラズ
マ、光等によるＣＶＤ法であることを特徴とするアルカ
リ電池。2. The alkaline battery according to claim 1, wherein the dry film formation method is a PVD method using vacuum deposition, sputtering, ion plating, or the like, or a CVD method using heat, plasma, light, or the like. Alkaline batteries.
を０．０１μｍ以上とするようにしたことを特徴とする
アルカリ電池。3. The alkaline battery according to claim 1, wherein the thickness of the metal or alloy having a hydrogen overvoltage higher than that of copper is set to 0.01 μm or more.
ズ、インジウム、ビスマスの１種以上の金属もしくは合
金であることを特徴とするアルカリ電池。4. The alkaline battery according to claim 1, wherein the metal or alloy having a higher hydrogen overpotential than copper is at least one metal or alloy of tin, indium, and bismuth.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392872A JP4166431B2 (en) | 2000-12-25 | 2000-12-25 | Alkaline battery |
| US09/947,978 US6794082B2 (en) | 2000-09-08 | 2001-09-06 | Alkaline battery |
| CNB011385227A CN1262031C (en) | 2000-09-08 | 2001-09-07 | Alkaline cell |
| EP01121474A EP1187236B1 (en) | 2000-09-08 | 2001-09-07 | Alkaline battery |
| DE60136680T DE60136680D1 (en) | 2000-09-08 | 2001-09-07 | Alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392872A JP4166431B2 (en) | 2000-12-25 | 2000-12-25 | Alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002198014A true JP2002198014A (en) | 2002-07-12 |
| JP4166431B2 JP4166431B2 (en) | 2008-10-15 |
Family
ID=18858789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000392872A Expired - Lifetime JP4166431B2 (en) | 2000-09-08 | 2000-12-25 | Alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4166431B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005259395A (en) * | 2004-03-10 | 2005-09-22 | Hitachi Maxell Ltd | Button type alkaline battery |
| JP2007080614A (en) * | 2005-09-13 | 2007-03-29 | Sony Corp | Alkaline battery |
| JP2007173220A (en) * | 2005-11-22 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Alkaline battery and method for producing the same |
-
2000
- 2000-12-25 JP JP2000392872A patent/JP4166431B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005259395A (en) * | 2004-03-10 | 2005-09-22 | Hitachi Maxell Ltd | Button type alkaline battery |
| JP4618771B2 (en) * | 2004-03-10 | 2011-01-26 | 日立マクセル株式会社 | Button-type alkaline battery |
| JP2007080614A (en) * | 2005-09-13 | 2007-03-29 | Sony Corp | Alkaline battery |
| JP2007173220A (en) * | 2005-11-22 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Alkaline battery and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4166431B2 (en) | 2008-10-15 |
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