JPH08213031A - Alkaline button battery - Google Patents
Alkaline button batteryInfo
- Publication number
- JPH08213031A JPH08213031A JP1678295A JP1678295A JPH08213031A JP H08213031 A JPH08213031 A JP H08213031A JP 1678295 A JP1678295 A JP 1678295A JP 1678295 A JP1678295 A JP 1678295A JP H08213031 A JPH08213031 A JP H08213031A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- indium
- current collector
- type alkaline
- 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.)
- Pending
Links
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はボタン形アルカリ電池に
関し、さらに詳しくは水銀を無添加とした場合にも電池
内部の水素ガス発生を抑制し、貯蔵中の性能劣化を防い
だ高性能なボタン形アルカリ電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a button-type alkaline battery, and more particularly to a high-performance button which suppresses hydrogen gas generation inside the battery even when mercury is not added and prevents performance deterioration during storage. Type alkaline battery.
【０００２】[0002]
【従来の技術】亜鉛を負極とするボタン形アルカリ電池
には、用途に応じて二酸化マンガン，酸化銀，あるいは
空気中の酸素を正極作用物質とする各種電池があり、こ
れら電池は、時計や補聴器，小型電子機器等に需要が拡
大している。2. Description of the Related Art Button-type alkaline batteries having zinc as a negative electrode include various batteries having manganese dioxide, silver oxide, or oxygen in the air as a positive electrode acting substance depending on the application. These batteries are used in watches and hearing aids. Demand is expanding for small electronic devices.
【０００３】従来、ボタン形に限らず亜鉛を負極とする
アルカリ電池にはゲル状亜鉛負極中に水銀が添加されて
いた。この水銀は、亜鉛合金粉や負極集電体の表面を覆
い、それらの水素過電圧を高めて水素ガスの発生を抑制
していた。Conventionally, mercury is added to the gel zinc negative electrode in alkaline batteries having zinc as the negative electrode, not limited to the button type. This mercury covered the surfaces of the zinc alloy powder and the negative electrode current collector, increased their hydrogen overvoltage, and suppressed the generation of hydrogen gas.
【０００４】しかしながら、近年の生活環境への関心の
高まりの中で、少量とはいえ有害な水銀が電池中に含有
されていることは問題であり、水銀を使用しない電池の
開発が望まれていた。However, with the recent growing interest in the living environment, the fact that a small amount of harmful mercury is contained in the battery is a problem, and the development of a battery that does not use mercury is desired. It was
【０００５】これらの電池に水銀を使用しなければ、当
然、亜鉛合金粉や負極集電体からの水素ガス発生が増大
し、電池の膨れや漏液、貯蔵中の大幅な性能劣化等の問
題が発生するため、これらへの対策が必要となる。そこ
で、これらの問題を解決するために、インジウム，ビス
マス，鉛等を添加した腐食しにくい亜鉛合金粉を使用し
たり、腐食抑制材としてインジウム化合物をゲル状亜鉛
負極に含有させたりした。また、亜鉛合金粉の腐食を抑
制する界面活性剤をゲル状亜鉛負極中に添加することも
提案されている。これらの技術は、すでに円筒形アルカ
リ乾電池では使われ、水銀無添加の電池が発売されてい
る。Unless mercury is used in these batteries, naturally, the generation of hydrogen gas from the zinc alloy powder and the negative electrode current collector will increase, causing problems such as battery swelling, liquid leakage, and drastic performance deterioration during storage. Therefore, it is necessary to take measures against them. Therefore, in order to solve these problems, a zinc alloy powder containing indium, bismuth, lead, etc., which does not corrode easily, is used, or an indium compound is contained in a gel zinc negative electrode as a corrosion inhibitor. It has also been proposed to add a surfactant that suppresses corrosion of zinc alloy powder to the gelled zinc negative electrode. These technologies have already been used in cylindrical alkaline dry batteries, and mercury-free batteries have been put on the market.
【０００６】[0006]
【発明が解決しようとする課題】ところが、円筒形アル
カリ電池では発生した水素ガスをある程度受け止められ
るスペースがあるが、ボタン形アルカリ電池ではこのス
ペースが無く、電池内部の水素ガスの発生がほとんど許
されない。そのために、円筒形アルカリ乾電池と同様の
技術をそのまま適用しても水素ガス発生の抑制が不十分
で、電池の膨れ等の問題を生じてしまう。However, the cylindrical alkaline battery has a space for receiving the generated hydrogen gas to some extent, but the button alkaline battery does not have this space and generation of hydrogen gas inside the battery is hardly permitted. . Therefore, even if the same technique as that for the cylindrical alkaline dry battery is applied as it is, the suppression of hydrogen gas generation is insufficient, and problems such as swelling of the battery occur.
【０００７】また、インジウム化合物や界面活性剤の含
有量を増やせば、水素ガス抑制の効果は大きくなるが、
電池性能に悪影響を及ぼしてしまい、特に界面活性剤は
一般的に悪影響が大きい上に効果を得るためには多量に
添加する必要があり、電池の電気特性や放電性能の悪化
につながってしまう。Further, if the content of the indium compound or the surfactant is increased, the effect of suppressing the hydrogen gas becomes large,
This adversely affects the battery performance, and in particular, the surfactant generally has a large adverse effect and needs to be added in a large amount in order to obtain the effect, which leads to deterioration of the electrical characteristics and discharge performance of the battery.
【０００８】さらに、これらの技術では亜鉛合金粉から
の水素ガス発生は抑制できても、負極集電体からの水素
ガス発生の抑制には効果がほとんどない。ボタン形アル
カリ電池では負極集電体からのガス発生も大きな問題で
あり、これを抑制することも必要である。Further, although these techniques can suppress the generation of hydrogen gas from the zinc alloy powder, they are hardly effective in suppressing the generation of hydrogen gas from the negative electrode current collector. In button-type alkaline batteries, gas generation from the negative electrode current collector is also a big problem, and it is also necessary to suppress it.
【０００９】本発明は、このような問題を解決するため
のもので、その目的は水銀を無添加にした場合にも電池
内部の水素ガスの発生を抑制し、性能劣化を防ぐことの
できる高性能なボタン形アルカリ電池を提供することに
ある。The present invention is intended to solve such a problem, and its purpose is to suppress the generation of hydrogen gas inside the battery even when mercury is not added, and to prevent performance deterioration. It is to provide a high performance button type alkaline battery.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するため
本発明者らは、ゲル状亜鉛負極中にインジウム化合物及
び特殊な界面活性剤を適量含有せしめた。またさらに改
良して、負極集電体のゲル状亜鉛負極との接触面をイン
ジウムまたはスズで被覆して電池内部のガス発生を抑制
することができた。In order to achieve the above object, the present inventors have added an appropriate amount of an indium compound and a special surfactant to a gelled zinc negative electrode. Further, by further improving, the contact surface of the negative electrode current collector with the gelled zinc negative electrode was coated with indium or tin, and gas generation inside the battery could be suppressed.
【００１１】すなわち本発明は負極ケースを兼ねた負極
集電体内に、亜鉛合金粉，アルカリ電解液およびゲル化
剤で構成されたゲル状亜鉛負極を有するボタン形アルカ
リ電池において、前記ゲル状亜鉛負極中に亜鉛合金粉に
対してインジウム０．０１〜０．１ｗｔ％化合物（イン
ジウムとして）および以下の構造式 Ｃn Ｆ2n+1−ＣＯＮＨ−（ＣＨ2 ＣＨ2 ０）m −ＣＯＮ
Ｈ−Ｃn Ｆ2n+1 ｎ：４〜１０ ｍ：２０〜１８０ で示される界面活性剤０．０２ｗｔ％以下を含有するこ
とを特徴とする。That is, the present invention provides a button type alkaline battery having a gelled zinc negative electrode composed of zinc alloy powder, an alkaline electrolyte and a gelling agent in a negative electrode current collector which also serves as a negative electrode case. indium 0.01 to 0.1% relative to compound zinc alloy powder during (as indium) and the following structural formula C n F 2n + 1 -CONH- ( CH 2 CH 2 0) m -CON
H-C n F 2n + 1 n: 4~10 m: characterized in that it contains a surfactant or less 0.02 wt% represented by 20 to 180.
【００１２】さらに本発明は上記ボタン形アルカリ電池
において、前記負極集電体の少なくともゲル状亜鉛負極
と接触する表面部分がインジウムまたはスズで被覆され
ていることを特徴とする。Further, the present invention is characterized in that, in the above button type alkaline battery, at least a surface portion of the negative electrode current collector which is in contact with the gelled zinc negative electrode is coated with indium or tin.
【００１３】またさらに本発明は、前記負極集電体が、
ニッケル−ステンレス−銅またはニッケル−鉄−銅の３
層クラッド材で構成されており、銅面へインジウムまた
はスズを無電解メッキで被覆した後、少なくともガスケ
ットとの接触部分に撥水処理剤を塗布したことを特徴と
する。Still further, in the present invention, the negative electrode current collector is
3 of nickel-stainless-copper or nickel-iron-copper
It is composed of a layer clad material, and is characterized in that after a copper surface is coated with indium or tin by electroless plating, a water repellent treatment agent is applied to at least a contact portion with the gasket.
【００１４】[0014]
【作用】本発明のボタン形アルカリ電池における水素ガ
ス発生抑制の明確な作用機構は分からないが、次のよう
に推察される。ゲル状亜鉛負極中において、インジウム
化合物は徐々に電解液に溶解してインジウムイオンとな
り、それらが亜鉛合金粉に触れてインジウムとして表面
に析出し、亜鉛合金粉の水素過電圧を高くして腐食しに
くくする。一方、界面活性剤は、亜鉛合金粉の表面を覆
い電解液との接触を制限して、腐食しにくくするが、本
発明で使用される構造式 Ｃn Ｆ2n+1−ＣＯＮＨ−（ＣＨ2 ＣＨ2 ０）m −ＣＯＮ
Ｈ−Ｃn Ｆ2n+1 ｎ：４〜１０ ｍ：２０〜１８０ の界面活性剤は、アルカリ電解液中で非常に安定である
ため、この効果が長期間安定して発揮される。The mechanism of hydrogen gas generation suppression in the button-type alkaline battery of the present invention is not clear, but it is presumed as follows. In the gelled zinc negative electrode, the indium compound gradually dissolves in the electrolytic solution to form indium ions, which come into contact with the zinc alloy powder and precipitate as indium on the surface, increasing the hydrogen overvoltage of the zinc alloy powder and making it less likely to corrode. To do. On the other hand, surfactants, zinc covers the surface of the alloy powder by limiting the contact with the electrolyte, although not easily corroded, structural formulas are employed in the present invention C n F 2n + 1 -CONH- ( CH 2 CH 2 0) m -CON
Since the surfactant of H—C n F 2n + 1 n: 4 to 10 m: 20 to 180 is very stable in the alkaline electrolyte, this effect is stably exhibited for a long period of time.
【００１５】ボタン形アルカリ電池では、インジウム化
合物と上記界面活性剤はどちらか一方のみではガス発生
抑制の効果が不十分であり、両者を適量含有すること
で、より大きな効果が得られる。In the button type alkaline battery, the effect of suppressing the gas generation is insufficient when only one of the indium compound and the above-mentioned surfactant is used, and a larger effect can be obtained by containing both indium compounds in an appropriate amount.
【００１６】インジウム化合物の含有量は、亜鉛合金粉
に対してインジウムとして０．０１〜０．１ｗｔ％であ
る。０．０１ｗｔ％より少ないとガス発生抑制の効果が
発揮されず、０．１ｗｔ％より多いと電池性能への影響
が大きくなって放電性能等が悪化する。また、界面活性
剤は極く僅かな量でも効果を発揮するが、含有量は最高
で亜鉛合金粉に対して０．０２ｗｔ％以下に限定され、
０．０２ｗｔ％より多く含有した場合、亜鉛合金粉の表
面に多量に付着し、電気特性や放電性能に大きな悪影響
を与えるばかりか、インジウム化合物の水素ガス発生抑
制機構も阻害し、効果が十分発揮されないため、かえっ
て水素ガス発生が増加してしまう。The content of the indium compound is 0.01 to 0.1 wt% as indium with respect to the zinc alloy powder. If it is less than 0.01 wt%, the effect of suppressing gas generation is not exerted, and if it is more than 0.1 wt%, the influence on the battery performance becomes large and the discharge performance and the like deteriorate. Further, the surfactant is effective even in a very small amount, but the content is limited to 0.02 wt% or less with respect to the zinc alloy powder,
If the content is more than 0.02 wt%, a large amount adheres to the surface of the zinc alloy powder, which not only has a great adverse effect on the electrical characteristics and discharge performance, but also inhibits the hydrogen gas generation suppressing mechanism of the indium compound and exerts the effect sufficiently. Since it is not carried out, hydrogen gas generation will rather increase.
【００１７】また、ゲル状亜鉛負極中のインジウム化合
物は、亜鉛合金同士の接触を良好にし、電池の内部抵抗
を低減させる働きもする。これは、界面活性剤の添加に
より少なからず起こる放電性能への悪影響を補い、より
性能を向上させる。The indium compound in the gelled zinc negative electrode also functions to improve the contact between zinc alloys and reduce the internal resistance of the battery. This compensates for the adverse effect on the discharge performance which occurs not a little due to the addition of the surfactant, and further improves the performance.
【００１８】一方、ボタン形アルカリ電池では、負極集
電体からの水素ガス発生の抑制も重要である。本発明で
は上記ボタン形アルカリ電池の水素ガス発生抑制効果を
さらに高めるため、負極集電体のゲル状亜鉛負極と接触
する部分を水素過電圧の高いインジウムまたはスズで被
覆する。これによって負極集電体からの水素ガスの発生
は抑制される。さらに、負極集電体成型時にできる表面
の傷等のガス発生の原因も、無電解メッキにより被覆さ
れ、ガス発生の抑制ができる。On the other hand, in the button type alkaline battery, it is also important to suppress the generation of hydrogen gas from the negative electrode current collector. In the present invention, in order to further enhance the hydrogen gas generation suppressing effect of the button-type alkaline battery, the portion of the negative electrode current collector that contacts the gel zinc negative electrode is coated with indium or tin having a high hydrogen overvoltage. This suppresses the generation of hydrogen gas from the negative electrode current collector. Further, the cause of gas generation such as scratches on the surface during molding of the negative electrode current collector is covered by electroless plating, and gas generation can be suppressed.
【００１９】また負極集電体にインジウムやスズを無電
解メッキで被覆するとアルカリ電解液が這い上がりやす
くなる傾向があるため、ガスケットと負極集電体の間か
らアルカリ電解液が漏液しやすくなってしまう。そこで
負極集電体に撥水処理剤を塗布し、ガスケットと負極集
電体の間にアルカリ電解液が進入するのを妨げ、漏液す
るのを防ぐ。そのため、少なくともガスケットと負極集
電体の接触部分に撥水処理剤を塗布するとよい。Further, if the negative electrode current collector is coated with indium or tin by electroless plating, the alkaline electrolyte tends to crawl up easily, so that the alkaline electrolyte easily leaks from between the gasket and the negative electrode current collector. Will end up. Therefore, a water repellent treatment agent is applied to the negative electrode current collector to prevent the alkaline electrolyte from entering between the gasket and the negative electrode current collector, and prevent leakage. Therefore, at least the contact portion between the gasket and the negative electrode current collector may be coated with the water repellent treatment agent.
【００２０】[0020]
【実施例】本発明の実施例を図面を参照して説明する。 （実施例１）図１は本発明の実施例であるＬＲ４４型ア
ルカリマンガン電池の断面図である。図１において、１
は負極集電体、２はゲル状亜鉛負極、３はセパレータ、
４は液保持材、５はガスケット、６は正極合剤、７は正
極ケースである。負極集電体１は図２に示すように、ニ
ッケル−ステンレス−銅またはニッケル−鉄−銅の３層
クラッド材で構成されており、銅面に無電解メッキでイ
ンジウムが被覆され、全面にフッ素系撥水処理剤が塗布
されている。An embodiment of the present invention will be described with reference to the drawings. (Embodiment 1) FIG. 1 is a sectional view of an LR44 type alkaline manganese battery which is an embodiment of the present invention. In FIG. 1, 1
Is a negative electrode current collector, 2 is a gelled zinc negative electrode, 3 is a separator,
4 is a liquid holding material, 5 is a gasket, 6 is a positive electrode mixture, and 7 is a positive electrode case. As shown in FIG. 2, the negative electrode current collector 1 is composed of a three-layer clad material of nickel-stainless-copper or nickel-iron-copper, and the copper surface is coated with indium by electroless plating. A water-repellent agent is applied.
【００２１】ゲル状亜鉛負極２は、亜鉛合金（アルミニ
ウム、インジウム、ビスマスを含有する）粉、３５ｗｔ
％水酸化カリウム水溶液、ポリアクリル酸および亜鉛合
金粉に対してインジウムとして０．０１ｗｔ％の酸化イ
ンジウムを攪拌混合し、この攪拌中に以下の構造式 Ｃn Ｆ2n+1−ＣＯＮＨ−（ＣＨ2 ＣＨ2 ０）m −ＣＯＮ
Ｈ−Ｃn Ｆ2n+1 ｎ：４〜１０ ｍ：２０〜１８０ で示される界面活性剤を亜鉛合金粉に対して０．００５
ｗｔ％滴下し、さらに攪拌混合して調製されたものであ
る。正極合剤６は、電解二酸化マンガンおよび鱗状黒鉛
を攪拌混合後、成形して調製されたものである。The gelled zinc negative electrode 2 is a zinc alloy (containing aluminum, indium and bismuth) powder, 35 wt.
% Aqueous solution of potassium hydroxide, a 0.01 wt% of indium oxide as indium mixed stirred against polyacrylic acid and zinc alloy powder, the following structural formula C n F 2n + 1 -CONH- during this stirring (CH 2 CH 2 0) m -CON
H—C n F 2n + 1 n: 4 to 10 m: a surfactant of 0.005 to 0.005 with respect to zinc alloy powder
It was prepared by dropping wt% of the mixture and further stirring and mixing. The positive electrode mixture 6 is prepared by stirring and mixing electrolytic manganese dioxide and scaly graphite, and then molding the mixture.
【００２２】（実施例２）酸化インジウムの含有量が亜
鉛合金粉に対してインジウムとして０．０５ｗｔ％であ
る以外は実施例１と同様にして、ＬＲ４４型アルカリマ
ンガン電池を作製した。(Example 2) An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the content of indium oxide was 0.05 wt% as indium based on the zinc alloy powder.
【００２３】（実施例３）酸化インジウムの含有量が亜
鉛合金粉に対してインジウムとして０．１ｗｔ％である
以外は実施例１と同様にして、ＬＲ４４型アルカリマン
ガン電池を作製した。(Example 3) An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the content of indium oxide was 0.1 wt% as indium based on the zinc alloy powder.
【００２４】（実施例４）界面活性剤の含有量が亜鉛合
金粉に対して０．００２ｗｔ％である以外は実施例２と
同様にして、ＬＲ４４型アルカリマンガン電池を作製し
た。(Example 4) An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the content of the surfactant was 0.002 wt% with respect to the zinc alloy powder.
【００２５】（実施例５）界面活性剤の含有量が亜鉛合
金粉に対して０．０１ｗｔ％である以外は実施例２と同
様にして、ＬＲ４４型アルカリマンガン電池を作製し
た。(Example 5) An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the content of the surfactant was 0.01 wt% with respect to the zinc alloy powder.
【００２６】（実施例６）界面活性剤の含有量が亜鉛合
金粉に対して０．０２ｗｔ％である以外は実施例２と同
様にして、ＬＲ４４型アルカリマンガン電池を作製し
た。(Example 6) An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the content of the surfactant was 0.02 wt% with respect to the zinc alloy powder.
【００２７】（実施例７）負極集電体に無電解メッキで
スズを被覆した以外は実施例１と同様にして、ＬＲ４４
型アルカリマンガン電池を作製した。Example 7 LR44 was carried out in the same manner as in Example 1 except that the negative electrode current collector was coated with tin by electroless plating.
Type alkaline manganese battery was prepared.
【００２８】（実施例８）負極集電体に無電解メッキで
スズを被覆した以外は実施例３と同様にして、ＬＲ４４
型アルカリマンガン電池を作製した。(Example 8) LR44 was carried out in the same manner as in Example 3 except that the negative electrode current collector was coated with tin by electroless plating.
Type alkaline manganese battery was prepared.
【００２９】（実施例９）負極集電体に無電解メッキで
スズを被覆した以外は実施例２と同様にして、ＬＲ４４
型アルカリマンガン電池を作製した。(Example 9) LR44 was carried out in the same manner as in Example 2 except that the negative electrode current collector was coated with tin by electroless plating.
Type alkaline manganese battery was prepared.
【００３０】（実施例１０）負極集電体に無電解メッキ
でスズを被覆した以外は実施例６と同様にして、ＬＲ４
４型アルカリマンガン電池を作製した。Example 10 LR4 was prepared in the same manner as in Example 6 except that the negative electrode current collector was coated with tin by electroless plating.
A 4-type alkaline manganese battery was produced.
【００３１】（比較例１）酸化インジウムの含有量が亜
鉛合金粉に対してインジウムとして０．００５ｗｔ％で
ある以外は実施例１と同様にして、ＬＲ４４型アルカリ
マンガン電池を作製した。Comparative Example 1 An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the content of indium oxide was 0.005 wt% as indium based on the zinc alloy powder.
【００３２】（比較例２）酸化インジウムの含有量が亜
鉛合金粉に対してインジウムとして０．２ｗｔ％である
以外は実施例１と同様にして、ＬＲ４４型アルカリマン
ガン電池を作製した。Comparative Example 2 An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the content of indium oxide was 0.2 wt% as indium based on the zinc alloy powder.
【００３３】（比較例３）界面活性剤の含有量が亜鉛合
金粉に対して０．０３ｗｔ％である以外は実施例２と同
様にして、ＬＲ４４型アルカリマンガン電池を作製し
た。Comparative Example 3 An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the content of the surfactant was 0.03 wt% with respect to the zinc alloy powder.
【００３４】（比較例４）ゲル状亜鉛負極中に界面活性
剤を含有していないこと以外は実施例３と同様にして、
ＬＲ４４型アルカリマンガン電池を作製した。(Comparative Example 4) The procedure of Example 3 was repeated except that the gelled zinc negative electrode contained no surfactant.
An LR44 type alkaline manganese battery was produced.
【００３５】（比較例５）ゲル状亜鉛負極中にインジウ
ム化合物を含有していないこと以外は実施例６と同様に
して、ＬＲ４４型アルカリマンガン電池を作製した。Comparative Example 5 An LR44 type alkaline manganese battery was produced in the same manner as in Example 6 except that the gelled zinc negative electrode did not contain an indium compound.
【００３６】（比較例６）ニッケル−ステンレス−銅の
３層クラッド材を負極集電体に成形した後、何も被覆せ
ずに撥水処理剤を塗布した以外は実施例２と同様にし
て、ＬＲ４４型アルカリマンガン電池を作製した。COMPARATIVE EXAMPLE 6 A nickel-stainless-copper three-layer clad material was molded into a negative electrode current collector, and then a water repellent agent was applied thereto without coating anything, and the same procedure as in Example 2 was performed. , LR44 type alkaline manganese battery was produced.
【００３７】（比較例７）酸化インジウムの含有量が亜
鉛合金粉に対してインジウムとして０．１ｗｔ％、界面
活性剤の含有量が亜鉛合金粉に対して０．０２ｗｔ％で
ある以外は比較例６と同様にして、ＬＲ４４型アルカリ
マンガン電池を作製した。(Comparative Example 7) Comparative Example except that the content of indium oxide was 0.1 wt% as indium with respect to the zinc alloy powder and the content of surfactant was 0.02 wt% with respect to the zinc alloy powder. In the same manner as in 6, an LR44 type alkaline manganese battery was produced.
【００３８】（比較例８）インジウム化合物および界面
活性剤をゲル状亜鉛負極中に含有しないこと以外は実施
例１と同様にして、ＬＲ４４型アルカリマンガン電池を
作製した。(Comparative Example 8) An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the indium compound and the surfactant were not contained in the gelled zinc negative electrode.
【００３９】（比較例９）インジウム化合物および界面
活性剤をゲル状亜鉛負極中に含有しないこと以外は実施
例７と同様にして、ＬＲ４４型アルカリマンガン電池を
作製した。Comparative Example 9 An LR44 type alkaline manganese battery was produced in the same manner as in Example 7 except that the gelled zinc negative electrode did not contain an indium compound and a surfactant.
【００４０】（比較例１０）ニッケル−ステンレス−銅
の３層クラッド材を負極集電体に成形した後、何も被覆
せずに撥水処理剤を塗布した以外は比較例８と同様にし
て、ＬＲ４４型アルカリマンガン電池を作製した。(Comparative Example 10) The procedure of Comparative Example 8 was repeated except that a nickel-stainless-copper three-layer clad material was molded into a negative electrode current collector and then coated with a water repellent agent without any coating. , LR44 type alkaline manganese battery was produced.
【００４１】（比較例１１）ニッケル−ステンレス−銅
の３層クラッド材を成形した負極集電体に、無電解メッ
キでインジウムを被覆した後、撥水処理剤を塗布しなか
った以外は実施例２と同様にして、ＬＲ４４型アルカリ
マンガン電池を作製した。(Comparative Example 11) Example 11 except that a negative electrode current collector formed by molding a nickel-stainless-copper three-layer clad material was coated with indium by electroless plating, and then no water repellent agent was applied. An LR44 type alkaline manganese battery was produced in the same manner as in 2.
【００４２】（比較例１２）ニッケル−ステンレス−銅
の３層クラッド材を成形した負極集電体に、無電解メッ
キでスズを被覆した後、撥水処理剤を塗布しなかった以
外は実施例９と同様にして、ＬＲ４４型アルカリマンガ
ン電池を作製した。(Comparative Example 12) An example was conducted except that a negative electrode current collector formed by molding a nickel-stainless-copper three-layer clad material was coated with tin by electroless plating and then no water repellent agent was applied. An LR44 type alkaline manganese battery was produced in the same manner as in No. 9.
【００４３】（比較例１３）ニッケル−ステンレス−銅
の３層クラッド材を負極集電体に成形した後、何も被覆
せずにそのまま使用した以外は実施例２と同様にして、
ＬＲ４４型アルカリマンガン電池を作製した。Comparative Example 13 The procedure of Example 2 was repeated except that a nickel-stainless-copper three-layer clad material was molded into a negative electrode current collector and used as it was without any coating.
An LR44 type alkaline manganese battery was produced.
【００４４】（比較例１４）亜鉛合金粉が鉛を含有し、
３％汞化したものである以外は比較例１０と同様にし
て、ＬＲ４４型アルカリマンガン電池を作製した。(Comparative Example 14) A zinc alloy powder contains lead,
An LR44 type alkaline manganese battery was produced in the same manner as in Comparative Example 10 except that the LR44 type was changed to 3%.
【００４５】以上のように作製した実施例及び比較例の
各試作電池を使用し、各種評価試験を行なった。各試験
は、対漏液試験は５０個、他の試験は２０個の平均値で
ある。Various evaluation tests were carried out using the prototype batteries of the examples and comparative examples produced as described above. Each test is an average value of 50 for leakage test and 20 for other tests.
【００４６】第１に実施例１〜１０、比較例１〜１０及
び比較例１４の各試作電池について、電池総高，開路電
圧及び内部抵抗を測定した。また１．３ｋΩ連続放電の
１．２Ｖまでの放電持続時間を測定し、本発明品の放電
性能を調査した。さらに、６０℃で４０時間貯蔵した
後、電池総高変化と開路電圧の劣化を測定するととも
に、１．３ｋΩ連続放電を行ない、放電性能の劣化を調
査した。これら６０℃貯蔵による変化量は、電池内部で
の水素ガスの発生量と相関し、変化量が小さいほど水素
ガスの発生量は少ない。結果を表１に示す。First, the total battery height, open circuit voltage, and internal resistance of the prototype batteries of Examples 1-10, Comparative Examples 1-10, and Comparative Example 14 were measured. The discharge duration of 1.2 kV of 1.3 kΩ continuous discharge was measured to investigate the discharge performance of the product of the present invention. Further, after being stored at 60 ° C. for 40 hours, the change in the total height of the battery and the deterioration of the open circuit voltage were measured, and 1.3 kΩ continuous discharge was performed to investigate the deterioration of the discharge performance. The amount of change due to storage at 60 ° C. correlates with the amount of hydrogen gas generated inside the battery, and the smaller the amount of change, the smaller the amount of hydrogen gas generated. The results are shown in Table 1.
【００４７】[0047]
【表１】 [Table 1]
【００４８】実施例１〜３，７，８及び比較例１，２の
結果によれば、インジウム化合物のゲル状亜鉛負極中の
含有量は０．０１〜０．１ｗｔ％が妥当であり、この範
囲からはずれた場合、水素ガス発生の抑制が不十分であ
ったり、放電性能に悪影響を与えたりする。According to the results of Examples 1 to 3, 7, 8 and Comparative Examples 1 and 2, it is appropriate that the content of the indium compound in the gelled zinc negative electrode is 0.01 to 0.1 wt%. If out of the range, the hydrogen gas generation is insufficiently suppressed or the discharge performance is adversely affected.
【００４９】実施例４〜６，９，１０及び比較例３の結
果によれば、アルカリ電解液中で安定な界面活性剤のゲ
ル状負極中の含有量は０．０２ｗｔ％以下が妥当であ
り、この範囲からはずれた場合、放電性能を著しく悪化
させる。According to the results of Examples 4 to 6, 9, 10 and Comparative Example 3, it is appropriate that the content of the surfactant stable in the alkaline electrolyte in the gelled negative electrode is 0.02 wt% or less. If it deviates from this range, the discharge performance will be significantly deteriorated.
【００５０】比較例４〜１０の結果によれば、ゲル状負
極亜鉛中へのインジウム化合物の含有、ゲル状負極亜鉛
中への界面活性剤の含有、負極集電体のゲル状亜鉛負極
と接触する部分へのインジウムまたはスズの被覆のいず
れが欠けた場合にも、本発明の目的は達成されず、水素
ガス発生の抑制が不十分となり電池総高の増加や、放電
性能の大幅な劣化を起こす。According to the results of Comparative Examples 4 to 10, inclusion of the indium compound in the gelled negative electrode zinc, inclusion of the surfactant in the gelled negative electrode zinc, contact with the gelled negative electrode of the negative electrode current collector. When either the coating of indium or tin on the portion to be covered is lacking, the object of the present invention is not achieved, the suppression of hydrogen gas generation is insufficient, and the total height of the battery increases and the discharge performance significantly deteriorates. Wake up.
【００５１】第２に実施例２，９と比較例６，１１〜１
４の各試作電池を、６０℃−９３％ＲＨで貯蔵し、高温
高湿下での耐漏液性試験を行ない、負極集電体への撥水
処理剤塗布の効果を調べた。電池内部での水素の発生が
多ければ耐漏液性は悪くなるが、負極集電体を電解液が
這い上がりやすければ、水素ガスの発生が少なくてもガ
スケットと負極集電体の間から漏液する。結果を表２に
示す。Secondly, Examples 2 and 9 and Comparative Examples 6 and 11 to 1
Each prototype battery of 4 was stored at 60 ° C.-93% RH, and a leak resistance test under high temperature and high humidity was conducted to examine the effect of applying the water repellent treatment agent to the negative electrode current collector. If the amount of hydrogen generated inside the battery is large, the resistance to liquid leakage will be poor, but if the electrolyte easily crawls over the negative electrode current collector, even if the amount of hydrogen gas generated is low, liquid will leak from between the gasket and the negative electrode current collector. To do. Table 2 shows the results.
【００５２】[0052]
【表２】 [Table 2]
【００５３】表２によれば本発明品の負極集電体を使用
した電池は明らかに耐漏液性に優れており、撥水処理剤
の塗布が耐漏液性を向上させることがわかる。なお、本
発明は上記実施例により限定されるものではない。すな
わち、上記実施例では、インジウム化合物は酸化インジ
ウムを使用しているが、これに限定されるものではな
く、水酸化インジウムや塩化インジウムであっても、本
発明による効果は得られる。From Table 2, it can be seen that the battery using the negative electrode current collector of the present invention is obviously excellent in liquid leakage resistance, and the application of the water repellent treatment improves liquid leakage resistance. The present invention is not limited to the above embodiments. That is, although indium oxide is used as the indium compound in the above embodiment, the present invention is not limited to this, and the effects of the present invention can be obtained even with indium hydroxide or indium chloride.
【００５４】また、本発明に使用される以下の構造式 Ｃn Ｆ2n+1−ＣＯＮＨ−（ＣＨ2 ＣＨ2 ０）m −ＣＯＮ
Ｈ−Ｃn Ｆ2n+1 ｎ：４〜１０ ｍ：２０〜１８０ で示される界面活性剤において、ｎ及びｍの数値が変わ
っても上記の範囲であれば効果に大きな変化はなく、同
様の結果が得られる。[0054] In addition, structural formulas of the following used in the present invention C n F 2n + 1 -CONH- ( CH 2 CH 2 0) m -CON
In the surfactant represented by H—C n F 2n + 1 n: 4 to 10 m: 20 to 180, even if the numerical values of n and m are changed, the effect is not significantly changed within the above range. The result is obtained.
【００５５】撥水処理剤についても同様であり、シリコ
ン系等、他の種類のものであってもかまわない。また塗
布方法も、負極集電体がガスケットと接触する部分に、
撥水処理剤が塗布されさえすればどのような塗布方法で
あってもかまわない。亜鉛合金粉等の他の要素について
も本発明の範囲を逸脱しない限り、変更して差し支えな
い。The same applies to the water repellent agent, and other types such as silicone type may be used. In addition, the coating method can also be applied to the part where the negative electrode current collector contacts the gasket.
Any application method may be used as long as the water repellent treatment agent is applied. Other elements such as zinc alloy powder may be changed without departing from the scope of the present invention.
【００５６】上記実施例ではボタン形アルカリマンガン
電池について説明したが、本発明はこれに限定されるも
のではなく、酸化銀電池，空気亜鉛電池等のゲル状亜鉛
を負極とする各種ボタン形アルカリ電池に適用できる。Although the button type alkaline manganese battery has been described in the above embodiment, the present invention is not limited to this, and various button type alkaline batteries such as silver oxide batteries and zinc-air batteries having gel zinc as a negative electrode are used. Applicable to
【００５７】[0057]
【発明の効果】以上説明したように、本発明のボタン形
アルカリ電池は、水銀を無添加にした場合においても電
池内部での水素ガスの発生を抑制し、貯蔵中の漏液や電
池の膨れ、性能劣化等の問題を解決できるので、水銀添
加電池と同等以上の性能が得られる。As described above, the button-type alkaline battery of the present invention suppresses the generation of hydrogen gas inside the battery even when mercury is not added, and leakage during storage and swelling of the battery occur. Since problems such as performance deterioration can be solved, performance equal to or higher than that of the mercury-added battery can be obtained.
【図１】本発明の実施例であるＬＲ４４型アルカリマン
ガン電池の断面図。FIG. 1 is a cross-sectional view of an LR44 type alkaline manganese battery that is an embodiment of the present invention.
【図２】図１のＡ部の拡大図。FIG. 2 is an enlarged view of part A in FIG.
１…負極集電体、２…ゲル状亜鉛負極、３…セパレー
タ、４…液保持材、５…ガスケット、６…正極合剤、７
…正極ケース。DESCRIPTION OF SYMBOLS 1 ... Negative electrode collector, 2 ... Gel zinc negative electrode, 3 ... Separator, 4 ... Liquid holding material, 5 ... Gasket, 6 ... Positive electrode mixture, 7
… Positive electrode case.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年３月２９日[Submission date] March 29, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４６[Correction target item name] 0046
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４６】第１に実施例１〜１０、比較例１〜１０及
び比較例１４の各試作電池について、電池総高，開路電
圧及び内部抵抗を測定した。また１．３ｋΩ連続放電の
１．２Ｖまでの放電持続時間を測定し、本発明品の放電
性能を調査した。さらに、６０℃で４０日間貯蔵した
後、電池総高変化と開路電圧の劣化を測定するととも
に、１．３ｋΩ連続放電を行ない、放電性能の劣化を調
査した。これら６０℃貯蔵による変化量は、電池内部で
の水素ガスの発生量と相関し、変化量が小さいほど水素
ガスの発生量は少ない。結果を表１に示す。First, the total battery height, open circuit voltage, and internal resistance of the prototype batteries of Examples 1-10, Comparative Examples 1-10, and Comparative Example 14 were measured. The discharge duration of 1.2 kV of 1.3 kΩ continuous discharge was measured to investigate the discharge performance of the product of the present invention. Furthermore, after being stored at 60 ° C. for 40 days , the change in the total height of the battery and the deterioration of the open circuit voltage were measured, and 1.3 kΩ continuous discharge was performed to investigate the deterioration of the discharge performance. The amount of change due to storage at 60 ° C. correlates with the amount of hydrogen gas generated inside the battery, and the smaller the amount of change, the smaller the amount of hydrogen gas generated. The results are shown in Table 1.
Claims (3)
鉛合金粉，アルカリ電解液およびゲル化剤で構成された
ゲル状亜鉛負極を有するボタン形アルカリ電池におい
て、前記ゲル状亜鉛負極中に亜鉛合金粉に対してインジ
ウム０．０１〜０．１ｗｔ％化合物（インジウムとし
て）および以下の構造式 Ｃn Ｆ2n+1−ＣＯＮＨ−（ＣＨ2 ＣＨ2 ０）m −ＣＯＮ
Ｈ−Ｃn Ｆ2n+1 ｎ：４〜１０ ｍ：２０〜１８０ で示される界面活性剤０．０２ｗｔ％以下を含有するこ
とを特徴とするボタン形アルカリ電池。1. A button type alkaline battery having a gelled zinc negative electrode composed of zinc alloy powder, an alkaline electrolyte and a gelling agent in a negative electrode current collector which also serves as a negative electrode case, wherein the gelled zinc negative electrode contains indium 0.01 to 0.1% relative to compound zinc alloy powder (as indium) and the following structural formula C n F 2n + 1 -CONH- ( CH 2 CH 2 0) m -CON
H-C n F 2n + 1 n: 4~10 m: button-type alkaline batteries, characterized in that it contains less surfactant 0.02 wt% represented by 20 to 180.
と接触する表面部分がインジウムまたはスズで被覆され
ている請求項１記載のボタン形アルカリ電池。2. The button type alkaline battery according to claim 1, wherein at least a surface portion of the negative electrode current collector, which is in contact with the gelled zinc negative electrode, is coated with indium or tin.
ス−銅またはニッケル−鉄−銅の３層クラッド材で構成
されており、その銅面へインジウムまたはスズを無電解
メッキで被覆した後、少なくともガスケットとの接触部
分に撥水処理剤を塗布したことを特徴とする請求項１記
載のボタン形アルカリ電池。3. The negative electrode current collector is composed of a three-layer clad material of nickel-stainless-copper or nickel-iron-copper, and after copper or copper is coated with indium or tin by electroless plating, The button-type alkaline battery according to claim 1, wherein a water repellent treatment agent is applied to at least a contact portion with the gasket.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1678295A JPH08213031A (en) | 1995-02-03 | 1995-02-03 | Alkaline button battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1678295A JPH08213031A (en) | 1995-02-03 | 1995-02-03 | Alkaline button battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08213031A true JPH08213031A (en) | 1996-08-20 |
Family
ID=11925767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1678295A Pending JPH08213031A (en) | 1995-02-03 | 1995-02-03 | Alkaline button battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08213031A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006228503A (en) * | 2005-02-16 | 2006-08-31 | Sony Corp | Alkaline battery |
| CN111742429A (en) * | 2018-03-23 | 2020-10-02 | 株式会社村田制作所 | Alkaline battery |
-
1995
- 1995-02-03 JP JP1678295A patent/JPH08213031A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006228503A (en) * | 2005-02-16 | 2006-08-31 | Sony Corp | Alkaline battery |
| CN111742429A (en) * | 2018-03-23 | 2020-10-02 | 株式会社村田制作所 | Alkaline battery |
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