JPH0785877A - Button type alkaline battery - Google Patents
Button type alkaline batteryInfo
- Publication number
- JPH0785877A JPH0785877A JP5248572A JP24857293A JPH0785877A JP H0785877 A JPH0785877 A JP H0785877A JP 5248572 A JP5248572 A JP 5248572A JP 24857293 A JP24857293 A JP 24857293A JP H0785877 A JPH0785877 A JP H0785877A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- zinc
- indium
- 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
- Cell Electrode Carriers And Collectors (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は負極に水銀を無添加とし
た場合、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 high-performance button type alkaline battery which suppresses hydrogen gas generation inside the battery and prevents performance deterioration during storage when mercury is not added to the negative electrode.
【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る。こ
れら電池は、従来の時計や補聴器等の用途に加えて、小
型電子機器、コードレス機器の発達によりメモリーバッ
クアップ等に需要が拡大している。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。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。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. In addition to conventional applications such as watches and hearing aids, demand for these batteries is expanding for memory backup and the like due to the development of small electronic devices and cordless devices. Conventionally, mercury is added to a gelled zinc negative electrode in alkaline batteries that use zinc as a negative electrode in addition 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. However, in recent years, with increasing interest in living environment, it is a problem that mercury, which is a small amount, is contained in the battery, and it has been desired to develop a battery that does not use mercury.
【０００３】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、腐食抑制剤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 increases, causing problems such as battery swelling, liquid leakage, and significant performance deterioration during storage. Therefore, it is necessary to take measures against them. Therefore, in order to solve these problems, a zinc alloy powder which does not corrode, to which indium, bismuth, lead, etc. are added 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.
【０００４】ところが、円筒形アルカリ乾電池では発生
した水素ガスをある程度受けと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 dry 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 of 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.
【０００５】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
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。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, if the content of the indium compound or the surfactant is increased, the effect of suppressing the hydrogen gas is increased,
This adversely affects the battery performance, and in particular, the surfactant 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. Furthermore, although these techniques can suppress the generation of hydrogen gas from the zinc alloy powder, they have almost no effect on 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.
【０００６】そこで、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アルカリ電解液中で安定な界面
活性剤を適量含有すると共に、負極集電体のゲル状亜鉛
負極と接触する表面部分をインジウムで被覆して、負極
集電体からの水素ガスの発生を抑制したボタン形アルカ
リ電池を提案している。Therefore, the present inventors have found that the gel-like zinc negative electrode contains an appropriate amount of an indium compound and a surfactant stable in an alkaline electrolyte, and the surface portion of the negative electrode current collector that comes into contact with the gel-like zinc negative electrode. We have proposed a button-type alkaline battery in which the indium is coated with indium to suppress the generation of hydrogen gas from the negative electrode current collector.
【０００７】[0007]
【発明が解決しようとする課題】ところが、インジウム
は高価な金属であるためキャップに被覆することはコス
トアップにつながってしまう。また、インジウムを被覆
するとアルカリ電解液が表面を這い上がり易くなり、電
池が少なからず漏液しやすくなる問題がある。さらに、
インジウムは柔らかい金属であるため、インジウムが被
覆された材料は加工時に成形型からの離れが悪くなり加
工性に影響してしまう。However, since indium is an expensive metal, covering the cap results in an increase in cost. In addition, when indium is coated, there is a problem that the alkaline electrolyte is likely to crawl up the surface, and the battery is likely to leak to some extent. further,
Since indium is a soft metal, the material coated with indium is difficult to separate from the mold during processing, which affects workability.
【０００８】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、性能劣化を防いだ高性
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 the deterioration of performance and to achieve high performance. It is to provide a button type alkaline battery.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
本発明は、負極ケースを兼ねた負極集電体内に、水銀無
添加亜鉛合金粉、アルカリ電解液、及びゲル化剤で構成
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、
インジウムとして０．０１〜０．１重量％のインジウム
化合物及びアルカリ電解液中で安定な界面活性剤０．０
１重量％以下を含有し、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スズ（Ｓｎ）である
ことを特徴とするボタン形アルカリ電池である。また、
前記界面活性剤がパーフルオロアルキル基を持つ構造で
あることを特徴としてもよい。In order to achieve the above object, the present invention provides a gel composed of a mercury-free zinc alloy powder, an alkaline electrolyte, and a gelling agent in a negative electrode current collector which also serves as a negative electrode case. In a button type alkaline battery having a zinc-like zinc negative electrode, with respect to zinc alloy powder in the gel-like zinc negative electrode,
0.01 to 0.1% by weight of indium compound as indium and surfactant stable in alkaline electrolyte 0.0
A button-type alkaline battery containing 1% by weight or less, wherein at least a surface portion of the negative electrode current collector that comes into contact with the gelled zinc negative electrode is tin (Sn). Also,
The surfactant may have a structure having a perfluoroalkyl group.
【００１０】[0010]
【作用】本発明のボタン形アルカリ電池において、その
明確な作用機構は明かでないが、次のように推察され
る。ゲル状亜鉛負極中に含有されるインジウム化合物及
びアルカリ電解液に安定な界面活性剤は、亜鉛合金粉の
腐食による水素ガスの発生を抑制するものである。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
金粉にふ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。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。In the button type alkaline battery of the present invention, the definite mechanism of action is not clear, but it is presumed as follows. The indium compound contained in the gelled zinc negative electrode and the surfactant stable in the alkaline electrolyte suppress generation of hydrogen gas due to corrosion of the zinc alloy powder. In the gel zinc negative electrode, the indium compound gradually dissolves in the electrolytic solution to form indium ions, which are in contact with the zinc alloy powder and deposited on the surface as indium, increasing the hydrogen overvoltage of the zinc alloy powder and making it less likely to corrode. To do. The surface-active agent covers the surface of the zinc alloy powder and limits the contact with the electrolytic solution to prevent corrosion.
【００１１】ボタン形アルカリ電池では、インジウム化
合物と界面活性剤はどちらか一方を含有したのではガス
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 if one of the indium compound and the surfactant is contained, and a larger effect can be obtained by containing an appropriate amount of both.
【００１２】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％に限
定され、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、放電性能等が悪化する。また、界面活性
剤の含有量は亜鉛合金粉に対して０．０１ｗｔ％以下に
限定され、０．０１ｗｔ％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
ガス抑制機構も阻害し、効果が充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。また、ゲル状
亜鉛負極中のインジウム化合物は、亜鉛合金粉同志等の
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 content of the indium compound is limited to 0.01 to 0.1 wt% as indium with respect to the zinc alloy powder, and if it is less than 0.01 wt%, the effect of suppressing gas generation is not exhibited and 0.1 wt% is not exhibited. If it is more than%, the battery performance is greatly affected, and the discharge performance and the like deteriorate. Further, the content of the surfactant is limited to 0.01 wt% or less with respect to the zinc alloy powder, and when it is more than 0.01 wt%, a large amount adheres to the surface of the zinc alloy powder, resulting in electrical characteristics and discharge performance. Not only has a great adverse effect on the hydrogen gas, but also inhibits the hydrogen gas suppression mechanism of the indium compound, so that the effect is not sufficiently exerted,
On the contrary, hydrogen gas generation will increase. Further, the indium compound in the gelled zinc negative electrode also functions to improve the contact between zinc alloy powders and the like and to 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.
【００１３】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が重要である。本発明品
は負極集電体のゲル状亜鉛負極と接触する部分が水素過
電圧の高いスズであるため、負極集電体からの水素ガス
の発生は抑制される。さらに電池内部でのガス発生が少
なくても、電解液が負極集電体を這いあがりガスケット
と負極集電体との間から漏液する場合があるが、スズは
アルカリ電解液の這いあがりが少ないので、このような
電池の漏液を防ぐ意味でも有効である。On the other hand, in button type alkaline batteries, it is important to suppress the generation of hydrogen gas from the negative electrode current collector. In the product of the present invention, since the portion of the negative electrode current collector that comes into contact with the gelled zinc negative electrode is tin with a high hydrogen overvoltage, generation of hydrogen gas from the negative electrode current collector is suppressed. In addition, even if there is little gas generation inside the battery, the electrolyte may crawl up the negative electrode current collector and leak from between the gasket and the negative electrode current collector, but tin does not crawl up to the alkaline electrolyte. Therefore, it is also effective in preventing such battery leakage.
【００１４】[0014]
【実施例】以下、本発明の実施例及び比較例を説明す
る。 （実施例１）ニッケル−ステンレス−銅の３層クラッド
材の銅面にスズを電気メッキで被覆し、これを図１に示
すようなＬＲ４４形アルカリマンガン電池用の負極ケー
ス１を兼ねた負極集電体に成形した。Ａ部を拡大して図
２に示した。一方、インジウム、ビスマス、アルミニウ
ムを含有する亜鉛合金粉、３５ｗｔ％水酸化カリウム水
溶液、ポリアクリル酸、亜鉛合金粉に対してインジウム
として０．０１ｗｔ％の酸化インジウム及び、亜鉛合金
粉に対して０．００３ｗｔ％のパーフルオロアルキルポ
リオキシエチレン系の界面活性剤を、攪拌混合してゲル
状亜鉛負極２を調製した。また、電解二酸化マンガン、
黒鉛を攪拌混合後成形して正極合剤６を調製した。EXAMPLES Examples and comparative examples of the present invention will be described below. (Example 1) The copper surface of a nickel-stainless-copper 3-layer clad material was coated with tin by electroplating, and this was also used as a negative electrode case 1 for an LR44 alkaline manganese battery as shown in FIG. It was molded into an electric body. The part A is enlarged and shown in FIG. On the other hand, zinc alloy powder containing indium, bismuth and aluminum, 35 wt% potassium hydroxide aqueous solution, polyacrylic acid, 0.01 wt% indium oxide as indium with respect to zinc alloy powder, and 0. A gel-type zinc negative electrode 2 was prepared by stirring and mixing 003 wt% perfluoroalkyl polyoxyethylene-based surfactant. Also, electrolytic manganese dioxide,
The positive electrode mixture 6 was prepared by molding graphite after stirring and mixing.
【００１５】上記負極集電体とゲル状亜鉛負極及び正極
合剤を用いて、図１に示すようなＬＲ４４形アルカリマ
ンガン電池を作製した。電池は正極ケース７内に正極合
剤６を充填し、セパレータ３と液保持材４を載置する。
一方負極ケース１内にゲル状亜鉛負極２を充填する。こ
れら両者をガスケット５を介して組合せ、正極ケース７
の開口端をプレスで内方へ折り曲げて密閉してなってい
る。An LR44 type alkaline manganese battery as shown in FIG. 1 was prepared using the above negative electrode current collector, gelled zinc negative electrode and positive electrode mixture. In the battery, the positive electrode case 7 is filled with the positive electrode mixture 6, and the separator 3 and the liquid holding material 4 are placed.
On the other hand, the gelled zinc negative electrode 2 is filled in the negative electrode case 1. Both of them are combined through a gasket 5 to form a positive electrode case 7
The open end of the is bent inward by a press and sealed.
【００１６】（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
ること以外は、実施例１と同様にしてＬＲ４４形アルカ
リマンガン電池を作製した。 （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％であること以外は、
実施例１と同様にしてＬＲ４４形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. (Example 3) Except that the content of indium oxide was 0.1 wt% as indium with respect to the zinc alloy powder,
An LR44 type alkaline manganese battery was produced in the same manner as in Example 1.
【００１７】（実施例４）パーフルオロアルキルポリオ
キシエチレン系の界面活性剤の含有量が、亜鉛合金粉に
対して０．００１ｗｔ％であること以外は、実施例２と
同様にしてＬＲ４４形アルカリマンガン電池を作製し
た。 （実施例５）パーフルオロアルキルポリオキシエチレン
系の界面活性剤の含有量が、亜鉛合金粉に対して０．０
０５ｗｔ％であること以外は、実施例２と同様にしてＬ
Ｒ４４形アルカリマンガン電池を作製した。 （実施例６）パーフルオロアルキルポリオキシエチレン
系の界面活性剤の含有量が、亜鉛合金粉に対して０．０
１ｗｔ％であること以外は、実施例２と同様にしてＬＲ
４４形アルカリマンガン電池を作製した。Example 4 An LR44 type alkali was prepared in the same manner as in Example 2 except that the content of the perfluoroalkylpolyoxyethylene-based surfactant was 0.001 wt% with respect to the zinc alloy powder. A manganese battery was produced. (Example 5) The content of the perfluoroalkylpolyoxyethylene-based surfactant was 0.0 based on the zinc alloy powder.
L in the same manner as in Example 2 except that the content is L.
An R44 type alkaline manganese battery was produced. (Example 6) The content of the perfluoroalkylpolyoxyethylene-based surfactant was 0.0 based on the zinc alloy powder.
LR was carried out in the same manner as in Example 2 except that it was 1 wt%.
A 44-type alkaline manganese battery was produced.
【００１８】（実施例７）酸化インジウムの変わりに水
酸化インジウムを用いたこと以外は、実施例２と同様に
してＬＲ４４形アルカリマンガン電池を作製した。 （実施例８）酸化インジウムの変わりに水酸化インジウ
ムを用いたこと以外は、実施例５と同様にしてＬＲ４４
形アルカリマンガン電池を作製した。(Example 7) An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that indium hydroxide was used instead of indium oxide. (Example 8) LR44 was carried out in the same manner as in Example 5 except that indium hydroxide was used instead of indium oxide.
A type alkaline manganese battery was prepared.
【００１９】（実施例９）パーフルオロアルキルポリオ
キシエチレン系の界面活性剤の変わりにポリオキシエチ
レン系の界面活性剤を用いたこと以外は、実施例２と同
様にしてＬＲ４４形アルカリマンガン電池を作製した。 （実施例１０）パーフルオロアルキルポリオキシエチレ
ン系の界面活性剤の変わりにポリオキシエチレン系の界
面活性剤を用いたこと以外は、実施例５と同様にしてＬ
Ｒ４４形アルカリマンガン電池を作製した。Example 9 An LR44 alkaline manganese battery was prepared in the same manner as in Example 2 except that a polyoxyethylene-based surfactant was used instead of the perfluoroalkylpolyoxyethylene-based surfactant. It was made. (Example 10) L was carried out in the same manner as in Example 5 except that a polyoxyethylene-based surfactant was used instead of the perfluoroalkylpolyoxyethylene-based surfactant.
An R44 type alkaline manganese battery was produced.
【００２０】（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
あること以外は、実施例１と同様にしてＬＲ４４形アル
カリマンガン電池を作製した。 （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％であること以外は、
実施例１と同様にしてＬＲ４４形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. (Comparative Example 2) Except that the content of indium oxide was 0.2 wt% as indium with respect to the zinc alloy powder,
An LR44 type alkaline manganese battery was produced in the same manner as in Example 1.
【００２１】（比較例３）パーフルオロアルキルポリオ
キシエチレン系の界面活性剤の含有量が、０．０１５ｗ
ｔ％である以外は、実施例２と同様にしてＬＲ４４形ア
ルカリマンガン電池を作製した。(Comparative Example 3) The content of the perfluoroalkylpolyoxyethylene-based surfactant was 0.015w.
An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the amount was t%.
【００２２】（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形アルカリマンガン電池を作製した。 （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５と同様にしてＬＲ４
４形アルカリマンガン電池を作製した。 （比較例６）ニッケル−ステンレス−銅の３層クラッド
材にスズを被覆せずそのまま成形した以外は、実施例２
と同様にしてＬＲ４４形アルカリマンガン電池を作製し
た。 （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％、パーフルオロアル
キルポリオキシエチレン系の界面活性剤の含有量が亜鉛
合金粉に対して０．０１ｗｔ％であること以外は、比較
例６と同様にしてＬＲ４４形アルカリマンガン電池を作
製した。 （比較例８）インジウム化合物及びアルカリ電解液中で
安定な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形アルカリマン
ガン電池を作製した。 （比較例９）ニッケル−ステンレス−銅の３層クラッド
材にスズを被覆せずそのまま成形した以外は、比較例８
と同様にしてＬＲ４４形アルカリマンガン電池を作製し
た。Comparative Example 4 An LR44 type alkaline manganese battery was produced in the same manner as in Example 3 except that the gelled zinc negative electrode did not contain a surfactant. (Comparative Example 5) LR4 was prepared in the same manner as in Example 5 except that the gelled zinc negative electrode did not contain an indium compound.
A 4 type alkaline manganese battery was produced. (Comparative Example 6) Example 2 except that the nickel-stainless-copper three-layer clad material was molded as it was without coating tin.
An LR44 type alkaline manganese battery was produced in the same manner as in. (Comparative Example 7) The content of indium oxide was 0.1 wt% as indium with respect to the zinc alloy powder, and the content of perfluoroalkylpolyoxyethylene-based surfactant was 0.01 wt% with respect to the zinc alloy powder. An LR44 type alkaline manganese battery was produced in the same manner as in Comparative Example 6 except that it was present. (Comparative Example 8) An LR44 type alkaline manganese battery was produced in the same manner as in Example 1 except that the gel zinc negative electrode did not contain an indium compound and a surfactant stable in an alkaline electrolyte. (Comparative Example 9) Comparative Example 8 except that the three-layer clad material of nickel-stainless-copper was molded as it was without coating tin.
An LR44 type alkaline manganese battery was produced in the same manner as in.
【００２３】（比較例１０）ニッケル−ステンレス−銅
の３層クラッド材の銅面にインジウムを電気メッキで被
覆した以外は、実施例２と同様にしてＬＲ４４形アルカ
リマンガン電池を作製した。 （比較例１１）ニッケル−ステンレス−銅の３層クラッ
ド材の銅面にインジウムを電気メッキで被覆した以外
は、実施例５と同様にしてＬＲ４４形アルカリマンガン
電池を作製した。Comparative Example 10 An LR44 type alkaline manganese battery was produced in the same manner as in Example 2 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by electroplating. (Comparative Example 11) An LR44 alkaline manganese battery was produced in the same manner as in Example 5 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by electroplating.
【００２４】（比較例１２）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９と同様にして
ＬＲ４４形アルカリマンガン電池を作製した。これらを
表１に示す。(Comparative Example 12) A zinc alloy powder contains lead,
An LR44 type alkaline manganese battery was produced in the same manner as in Comparative Example 9 except that the LR44 type was changed to 3%. These are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】以上のように作製した実施例及び比較例の
各試作電池の電池総高、開路電圧（ＯＶ）及び内部抵抗
（Ｉｍｐ）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発生
量は少ない。また、試作電池を６０℃−９３％ＲＨで貯
蔵し、耐漏液性試験を行なった。電池内部での水素ガス
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
くてもパッキングと負極集電体の間から漏液する。表
２，３にこれら試験結果を示す。試験結果は全て２０個
の平均値である。The total battery height, open circuit voltage (OV) and internal resistance (Imp) of the prototype batteries of the examples and comparative examples produced as described above were measured. Moreover, 1.k of 1.3 kΩ continuous discharge.
The discharge duration of up to 2 V 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.
A continuous discharge of 3 kΩ was performed to investigate the deterioration of 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. Further, the prototype battery was stored at 60 ° C.-93% RH, and a leak resistance test was conducted. If the amount of hydrogen gas generated inside the battery is large, the resistance to liquid leakage is poor, but if the electrolyte easily crawls over the negative electrode current collector, even if the amount of hydrogen gas generated is small, leakage will occur between the packing and the negative electrode current collector. To liquidate. Tables 2 and 3 show the results of these tests. All test results are average values of 20 pieces.
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】表２，３より明らかなように、実施例１〜
３及び比較例１，２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。実施例４〜６，９，１０及び比較例３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亜鉛負極中
の含有量は０．０１ｗｔ％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。As is clear from Tables 2 and 3, Examples 1 to 1
According to No. 3 and Comparative Examples 1 and 2, the content of the indium compound in the gel zinc negative electrode is properly 0.01 to 0.1 wt%, and when it deviates from this range, the suppression of hydrogen gas generation is inadequate. It may be sufficient or may adversely affect the discharge performance. According to Examples 4 to 6, 9 and 10 and Comparative Example 3, it is appropriate that the content of the surfactant stable in the alkaline electrolyte in the gelled zinc negative electrode is 0.01 wt% or less. If it comes off, the discharge performance is significantly deteriorated.
【００３０】比較例４〜９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。また、実施例２，５及び比較例１０，１１によれ
ば、ゲル状亜鉛負極と接触する部分をスズで被覆した負
極集電体を使用する本発明品は、ゲル状亜鉛負極と接触
する部分をインジウムで被覆した負極集電体を使用する
電池と同等の水素ガス発生の抑制効果を有し、耐漏液性
はより優れている。According to Comparative Examples 4 to 9, inclusion of the indium compound in the gelled negative electrode zinc, inclusion of the surfactant in the gelled negative electrode zinc, and the portion of the negative electrode current collector that comes into contact with the gelled zinc negative electrode. If any of the tin coatings on the metal is lacking, the object of the present invention is not achieved, the suppression of hydrogen gas generation becomes insufficient, and the total height of the battery increases and the discharge performance significantly deteriorates. Further, according to Examples 2 and 5 and Comparative Examples 10 and 11, the product of the present invention using the negative electrode current collector in which the portion contacting the gel zinc negative electrode is coated with tin is the portion contacting the gel zinc negative electrode. It has the same effect of suppressing the generation of hydrogen gas as a battery using a negative electrode current collector coated with indium, and is more excellent in liquid leakage resistance.
【００３１】なお、本発明は上記実施例により限定され
る物ではない。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及び水酸化インジウム、界面活
性剤はパーフルオロアルキルポリオキシエチレン系及び
ポリオキシエチレン系を使用しているが、ともにこれに
限定されるものではなく、インジウム化合物及び界面活
性剤が他のものであっても、本発明による効果は得られ
る。また、上記実施例ではニッケル−ステンレス−銅の
３層クラッド材の銅面にスズを電気メッキで被覆した後
に負極集電体に加工する方法を示したが、本発明はこれ
に限定されるものではなく、負極集電体に加工した後に
スズを被覆しても差し支えなく、無電解メッキ等の他の
方法での被覆や材料自体にスズ層があるクラッド材を用
いても本発明の効果は得られる。The present invention is not limited to the above embodiment. That is, in the above examples, the indium compound uses indium oxide and indium hydroxide, and the surfactant uses perfluoroalkylpolyoxyethylene-based and polyoxyethylene-based, but both are not limited to this. Even if other indium compounds and surfactants are used, the effects of the present invention can be obtained. Further, in the above-mentioned examples, the method of processing the negative electrode current collector after coating the copper surface of the nickel-stainless-copper three-layer clad material with electroplating was shown, but the present invention is not limited to this. Instead, it may be coated with tin after being processed into the negative electrode current collector, and the effect of the present invention can be obtained even by coating with another method such as electroless plating or using a clad material having a tin layer as the material itself. can get.
【００３２】亜鉛合金粉等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。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て起用できることは勿論である。Elements such as zinc alloy powder may be changed without departing from the scope of the present invention. Although the button-type alkaline manganese battery has been described in the above embodiment, the present invention is not limited to this, and is used in various button-type alkaline batteries such as silver oxide battery and zinc-air battery having gel zinc as a negative electrode. Of course you can.
【００３３】[0033]
【発明の効果】以上の説明のごとく、本発明によって作
製された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、水銀を添加した電池と同等以上の性能が得られ
る。As described above, the button-type alkaline battery manufactured according to the present invention suppresses the generation of hydrogen gas inside the battery even when mercury is not added, and prevents leakage of liquid during storage. It is possible to solve problems such as swelling of a battery, swelling of a battery, and performance deterioration, and a performance equal to or higher than that of a battery to which mercury is added can be obtained.
【図１】本発明の実施例であるＬＲ４４形ボタン形アル
カリ電池の断面図である。FIG. 1 is a cross-sectional view of an LR44 type button alkaline battery that is an embodiment of the present invention.
【図２】本発明の負極ケースを兼ねた集電体の図１Ａ部
の拡大断面図である。FIG. 2 is an enlarged cross-sectional view of a portion of FIG. 1A of a current collector that also serves as a negative electrode case of the present invention.
１ 負極ケース ２ ゲル状亜鉛負極 ６ 正極合剤 ７ 正極ケース 1 Negative electrode case 2 Gel-like zinc negative electrode 6 Positive electrode mixture 7 Positive electrode case
Claims (2)
銀無添加亜鉛合金粉、アルカリ電解液、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
インジウムとして、０．０１〜０．１重量％のインジウ
ム化合物と、アルカリ電解液中で安定な界面活性剤０．
０１重量％以下とを含有し、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スズであること
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 a mercury-free zinc alloy powder, an alkaline electrolyte, and a gelling agent in a negative electrode current collector that also serves as a negative electrode case. 0.01 to 0.1 wt% of indium compound as indium with respect to zinc alloy powder in the negative electrode, and a surfactant that is stable in an alkaline electrolyte.
0.1 wt% or less, and at least the surface portion of the negative electrode current collector that comes into contact with the gelled zinc negative electrode is tin, and a button type alkaline battery.
ル基を持つ構造である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。2. The button type alkaline battery according to claim 1, wherein the surfactant has a structure having a perfluoroalkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5248572A JPH0785877A (en) | 1993-09-10 | 1993-09-10 | Button type alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5248572A JPH0785877A (en) | 1993-09-10 | 1993-09-10 | Button type alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0785877A true JPH0785877A (en) | 1995-03-31 |
Family
ID=17180139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5248572A Pending JPH0785877A (en) | 1993-09-10 | 1993-09-10 | Button type alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0785877A (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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6459769A (en) * | 1987-08-31 | 1989-03-07 | Alkali Dry Battery Eng Lab | Negative current collector for zinc-alkaline battery |
| JPH0279367A (en) * | 1988-07-25 | 1990-03-19 | Cipel | Electrochemical battery equipped with alkaline electrolyte and zinc negative electrode |
| JPH02267856A (en) * | 1989-04-07 | 1990-11-01 | Matsushita Electric Ind Co Ltd | Alkaline battery |
| JPH0513070A (en) * | 1991-07-02 | 1993-01-22 | Hitachi Maxell Ltd | Alkaline battery |
| JPH05182658A (en) * | 1991-12-28 | 1993-07-23 | Sanyo Electric Co Ltd | Manufacture of negative electrode collector for zinc alkaline battery |
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
-
1993
- 1993-09-10 JP JP5248572A patent/JPH0785877A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6459769A (en) * | 1987-08-31 | 1989-03-07 | Alkali Dry Battery Eng Lab | Negative current collector for zinc-alkaline battery |
| JPH0279367A (en) * | 1988-07-25 | 1990-03-19 | Cipel | Electrochemical battery equipped with alkaline electrolyte and zinc negative electrode |
| JPH02267856A (en) * | 1989-04-07 | 1990-11-01 | Matsushita Electric Ind Co Ltd | Alkaline battery |
| JPH0513070A (en) * | 1991-07-02 | 1993-01-22 | Hitachi Maxell Ltd | Alkaline battery |
| JPH05182658A (en) * | 1991-12-28 | 1993-07-23 | Sanyo Electric Co Ltd | Manufacture of negative electrode collector for zinc alkaline battery |
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
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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