JP3522303B2 - Button type alkaline battery - Google Patents
Button type alkaline batteryInfo
- Publication number
- JP3522303B2 JP3522303B2 JP12576893A JP12576893A JP3522303B2 JP 3522303 B2 JP3522303 B2 JP 3522303B2 JP 12576893 A JP12576893 A JP 12576893A JP 12576893 A JP12576893 A JP 12576893A JP 3522303 B2 JP3522303 B2 JP 3522303B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- indium
- battery
- zinc
- current collector
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y02E60/12—
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用
の負極ケースを兼ねた負極集電体に関し、さらに詳しく
は水銀を添加しないボタン形アルカリ電池に使用しても
水素ガスの発生を抑制できる負極集電体及び、これを用
いて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 negative electrode current collector that also serves as a negative electrode case for a button type alkaline battery, and more specifically, can suppress generation of hydrogen gas even when used in a button type alkaline battery containing no added mercury. The present invention relates to a negative electrode current collector and a high-performance button-type alkaline battery using the same to prevent performance deterioration during storage.
【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。2. Description of the Related Art Button-type alkaline batteries using zinc as a negative electrode include various batteries using 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.
【０００３】従来、ボタン形に限らず亜鉛粉を負極とす
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 gelled zinc negative electrode in alkaline batteries having zinc powder 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】一方、近年生活環境への関心が高まり、少
量とはいえ水銀が電池中に含有されていることは問題で
あり、水銀を添加しない電池の開発が望まれていた。On the other hand, in recent years, interest in the living environment has increased, and it is a problem that mercury is contained in the battery even though it is a small amount, and it has been desired to develop a battery in which mercury is not added.
【０００５】ところで、電池に水銀を添加しなければ、
当然、亜鉛合金粉や負極集電体からの水素ガスの発生が
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。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ている。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、既に円
筒形アルカリ乾電池では使われ、水銀を添加しない電池
として発売されている。By the way, unless mercury is added to the battery,
Naturally, the generation of hydrogen gas from the zinc alloy powder and the negative electrode current collector increases, which causes problems such as swelling and leakage of the battery, and drastic performance deterioration during storage. In order to solve these problems, a zinc alloy powder that does not corrode to which indium, bismuth, lead, etc. are added is used, or an indium compound is contained in the 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 have been put on the market as mercury-free batteries.
【０００６】しかしながら、ボタン形アルカリ電池は、
円筒形アルカリ乾電池のように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なく、従って電池内部の
水素ガス発生は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
素ガスの発生の抑制が不十分で、電池の膨れ等を生じて
しまう。However, the button type alkaline battery is
Unlike a cylindrical alkaline dry battery, there is no space to receive the generated hydrogen gas to some extent, and therefore hydrogen gas generation 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 generation of hydrogen gas is not sufficiently suppressed, and the battery swells.
【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、水素ガスの抑制効果は大きくなるが、
電池性能に影響を及ぼしてしまい、特に界面活性剤は効
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 affects the battery performance, and in particular, a surfactant needs to be added in a large amount to obtain the effect, which leads to deterioration of the electrical characteristics and discharge performance of the battery.
【０００８】さらに、これらの技術により亜鉛合金粉か
らの水素ガスの発生は抑制できても、負極集電体からの
水素ガスの発生には効果がほとんどなく、また、ボタン
形アルカリ電池ではその形状からみて電池内部にスペー
スがとれないので、負極集電体からのガス発生の抑制
は、電池の安全性および電池性能の維持からも必要なこ
とである。Further, although these techniques can suppress the generation of hydrogen gas from the zinc alloy powder, they have almost no effect on the generation of hydrogen gas from the negative electrode current collector, and the shape of the button type alkaline battery is Since no space can be taken inside the battery from the viewpoint of view, suppression of gas generation from the negative electrode current collector is necessary from the viewpoint of safety of the battery and maintenance of battery performance.
【０００９】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ともに、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.
【００１０】[0010]
【発明が解決しようとする課題】ところで、本発明者等
が提案した負極集電体は、インジウムの被覆が薄いとガ
ス発生抑制効果が低く不安定であり、インジウムの被覆
が厚い方がより高いガス発生抑制効果が安定して得られ
る。しかし、インジウムが厚すぎると、電気特性や放電
性能に悪影響を与え、またインジウムの被覆が厚いとア
ルカリ電解液が這い上がり易くなり、漏液し易くなると
いう問題がある。さらに、インジウムが厚く被覆された
材料は加工時に成形型からの離れが悪くなり、加工性に
も問題がある。それに、インジウムは高価な金属である
ため厚く被覆することはコストアップにつながるという
問題がある。By the way, in the negative electrode current collector proposed by the present inventors, when the indium coating is thin, the gas generation suppressing effect is low and unstable, and the thicker the indium coating is, the higher. The gas generation suppressing effect is stably obtained. However, if the indium is too thick, the electrical characteristics and discharge performance will be adversely affected, and if the indium coating is thick, the alkaline electrolyte will tend to crawl up and the liquid will leak easily. Further, a material coated with thick indium is difficult to separate from the mold during processing, and there is a problem in workability. In addition, since indium is an expensive metal, there is a problem that a thick coating leads to cost increase.
【００１１】本発明は、このような問題を解決するため
になされたもので、その目的は水銀を添加しないボタン
形アルカリ電池に使用しても水素ガスの発生を抑制でき
る負極集電体、及びこれを用いて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を提供することにあ
る。The present invention has been made to solve such a problem, and its object is to provide a negative electrode current collector capable of suppressing the generation of hydrogen gas even when used in a button type alkaline battery containing no mercury, and The purpose of this is to provide a high-performance button-type alkaline battery that prevents performance deterioration during storage.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するた
め、本発明の請求項１は、亜鉛合金粉，アルカリ電解
液，及びゲル化剤で構成された水銀無添加のゲル状亜鉛
負極を有するボタン形アルカリ電池において、負極ケー
スを兼ねた負極集電体の少なくともゲル状亜鉛負極と接
触する表面部分に厚さ０．５〜３．５μｍのインジウム
が存在しており、かつ水銀無添加の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
ｗｔ％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０．０１ｗｔ％以下を含有することを特徴
とする。また、請求項２は、請求項１のボタン形アルカ
リ電池において、負極ケースを兼ねた負極集電体が、成
形後に負極ケース内面となる側に予めインジウムを電気
メッキした原材料を成形加工したものであることを特徴
とする。In order to achieve the above object, claim 1 of the present invention comprises a mercury-free gelled zinc negative electrode composed of a zinc alloy powder, an alkaline electrolyte and a gelling agent. In a button-type alkaline battery, indium having a thickness of 0.5 to 3.5 μm is present in at least the surface portion of the negative electrode current collector that also serves as the negative electrode case and is in contact with the gelled zinc negative electrode, and the mercury-free gel is used. 0.01 to 0.1 as indium with respect to zinc alloy powder in the zinc oxide negative electrode
It is characterized by containing a wt% indium compound and 0.01 wt% or less of a surfactant stable in an alkaline electrolyte. Also, claim 2 is a button-shaped arc of claim 1.
In the rechargeable battery, the negative electrode current collector that also serves as the negative electrode case is characterized by being formed by processing a raw material in which indium is electroplated in advance on the side to be the negative electrode case inner surface after molding.
【００１３】[0013]
【作用】ボタン形アルカリ電池では、負極集電体からの
水素ガスの発生を抑制することは重要である。負極集電
体のゲル状亜鉛負極と接触する表面部分に被覆されたイ
ンジウムは、負極集電体表面の水素過電圧を高くし、水
素ガスの発生を抑制するが、そのインジウム被覆の厚さ
は０．５〜３．５μｍに限定される。すなわち、インジ
ウム被覆の厚さが０．５μｍよりも薄いと水素ガスの発
生抑制効果は十分に発揮されず、３．５μｍよりも厚い
と水素ガスの抑制効果は高く安定するが、電池の電気特
性や放電性能に悪影響を及ぼすうえに電解液の這い上が
り現象が助長されるため漏液しやすくなる。In the button type alkaline battery, it is important to suppress the generation of hydrogen gas from the negative electrode current collector. The indium coated on the surface of the negative electrode current collector in contact with the gel zinc negative electrode increases the hydrogen overvoltage on the surface of the negative electrode current collector and suppresses the generation of hydrogen gas, but the thickness of the indium coating is 0. It is limited to 0.5 to 3.5 μm. That is, if the thickness of the indium coating is less than 0.5 μm, the hydrogen gas generation suppressing effect is not sufficiently exerted, and if it is thicker than 3.5 μm, the hydrogen gas suppressing effect is high and stable, but the electrical characteristics of the battery are high. In addition to adversely affecting the discharge performance and facilitating the creeping-up phenomenon of the electrolyte, the electrolyte easily leaks.
【００１４】また、インジウム被覆の方法としては、電
気メッキ、溶融メッキ、無電解メッキ等があるが、溶融
メッキや無電解メッキでは、インジウム被膜を薄く抑制
することが難しいので、電気メッキが有利である。そし
て、製造工程上、インジウムを予め被覆した材料を成形
加工する方法が簡潔で有利であるが、その際インジウム
被覆が厚いと成形型からの離れが悪くなる。これはイン
ジウムが軟らかい金属であるためで、これもインジウム
被覆の厚さを限定することで加工性への影響はなくな
る。Further, as a method of indium coating, there are electroplating, hot dipping, electroless plating and the like. However, electroplating is advantageous because it is difficult to suppress the indium coating thin by hot dipping or electroless plating. is there. From the viewpoint of the manufacturing process, the method of forming and processing a material precoated with indium is simple and advantageous, but if the indium coating is thick at this time, the separation from the molding die becomes poor. This is because indium is a soft metal, and by limiting the thickness of the indium coating, this also does not affect workability.
【００１５】さらに、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に安定な界面活性剤を含有する
ことで、亜鉛合金粉の腐食による水素ガスの発生を抑制
する。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
食しにくくしている。Furthermore, by containing an indium compound and a surfactant stable in the alkaline electrolyte in the gel zinc negative electrode, generation of hydrogen gas due to corrosion of the zinc alloy powder is suppressed. 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 deposit on the surface, increasing the hydrogen overvoltage of the zinc alloy powder and making it less likely to corrode. The surfactant is
The surface of the zinc alloy powder is covered to limit contact with the electrolytic solution to prevent corrosion.
【００１６】[0016]
【実施例】以下、本発明の実施例及び比較例について詳
細に説明する。
（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、インジウムを電気メッキで０．５μｍ被覆
し、これを図１に示すようなＬＲ４４アルカリマンガン
電池用の負極ケースを兼ねた負極集電体１に成形した。
図２は、図１のＡ部分の拡大図であり、ニッケル−ステ
ンレス−銅の３層クラッド材の銅面に、インジウムを被
覆されていることが分る。EXAMPLES Examples of the present invention and comparative examples will be described in detail below. (Example 1) A copper surface of a nickel-stainless-copper three-layer clad material was coated with indium by 0.5 μm by electroplating, which also served as a negative electrode case for an LR44 alkaline manganese battery as shown in FIG. It was molded into a negative electrode current collector 1.
FIG. 2 is an enlarged view of a portion A in FIG. 1, and it can be seen that the copper surface of the nickel-stainless steel-copper three-layer clad material is coated with indium.
【００１７】一方、アルミニウム，インジウム，ビスマ
ス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５００ｐｐｍの酸化インジウム及び亜鉛合金粉に
対して３０ｐｐｍ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撹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，黒鉛を撹拌混
合後成形して正極合剤６を調製した。そして、この負極
集電体１とゲル状亜鉛負極２及び正極合剤６を用いて、
図１に示すようなＬＲ４４アルカリマンガン電池を作成
した。なお、図１において、３はセパレータ、４は液保
持材、５はガスケット、７は正極ケースである。On the other hand, zinc alloy powder containing aluminum, indium and bismuth, 35 wt% potassium hydroxide aqueous solution, polyacrylic acid, zinc alloy powder with indium oxide of 500 ppm as indium and zinc alloy powder with 30 ppm of par. Fluoroalkyl polyoxyethylene-based surfactant is stirred and mixed to form a gelled zinc negative electrode 2
Was prepared. Further, electrolytic manganese dioxide and graphite were mixed by stirring and then molded to prepare a positive electrode mixture 6. Then, using the negative electrode current collector 1, the gelled zinc negative electrode 2 and the positive electrode mixture 6,
An LR44 alkaline manganese battery as shown in FIG. 1 was prepared. In FIG. 1, 3 is a separator, 4 is a liquid holding material, 5 is a gasket, and 7 is a positive electrode case.
【００１８】（実施例２）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
１．０μｍ被覆したこと以外は、実施例１と同様のＬＲ
４４アルカリマンガン電池を作製した。Example 2 The same LR as in Example 1 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by 1.0 μm by electroplating.
A 44 alkaline manganese battery was prepared.
【００１９】（実施例３）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
２．０μｍ被覆したこと以外は、実施例１と同様のＬＲ
４４アルカリマンガン電池を作製した。Example 3 The same LR as in Example 1 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by 2.0 μm by electroplating.
A 44 alkaline manganese battery was prepared.
【００２０】（実施例４）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
３．５μｍ被覆したこと以外は、実施例１と同様のＬＲ
４４アルカリマンガン電池を作製した。Example 4 The same LR as in Example 1 except that the copper surface of the nickel-stainless-copper 3-layer clad material was coated with indium by 3.5 μm by electroplating.
A 44 alkaline manganese battery was prepared.
【００２１】（比較例１）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
０．２μｍ被覆したこと以外は、実施例１と同様のＬＲ
４４アルカリマンガン電池を作製した。Comparative Example 1 The same LR as in Example 1 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by 0.2 μm by electroplating.
A 44 alkaline manganese battery was prepared.
【００２２】（比較例２）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
４．０μｍ被覆したこと以外は、実施例１と同様のＬＲ
４４アルカリマンガン電池を作製した。(Comparative Example 2) An LR similar to that of Example 1 except that the copper surface of the nickel-stainless-copper three-layer clad material was coated with indium by 4.0 μm by electroplating.
A 44 alkaline manganese battery was prepared.
【００２３】（比較例３）ニッケル−ステンレス−銅の
３層クラッド材の銅面に、インジウムを被覆していない
以外は、実施例１と同様のＬＲ４４アルカリマンガン電
池を作製した。(Comparative Example 3) An LR44 alkaline manganese battery similar to that of Example 1 was prepared except that the copper surface of the nickel-stainless-copper three-layer clad material was not coated with indium.
【００２４】（比較例４）亜鉛合金粉として、鉛を含有
し３％の水銀をアマルガムしたものを用い、３５ｗｔ％
水酸化カリウム水溶液及びポリアクリル酸とともに撹拌
混合してゲル状亜鉛負極を調製した。このゲル状亜鉛負
極を用いた以外は比較例３と同様のＬＲ４４アルカリマ
ンガン電池を作製した。(Comparative Example 4) A zinc alloy powder containing lead and containing amalgam of 3% mercury was used.
A gelled zinc negative electrode was prepared by stirring and mixing with an aqueous potassium hydroxide solution and polyacrylic acid. An LR44 alkaline manganese battery similar to that of Comparative Example 3 was prepared except that this gelled zinc negative electrode was used.
【００２５】以上のように作成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、本発明電池の放電性能を調査した。The battery total height, open circuit voltage and internal resistance of each prototype battery of the example and the comparative example prepared as described above were measured. The discharge duration of 1.2 kV continuous discharge up to 1.2 V was measured to investigate the discharge performance of the battery of the present invention.
【００２６】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。Further, 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.
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.
【００２７】また、試作電池を４５℃−９３％ＲＨで貯
蔵し、耐漏液性試験を行った。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電解液が漏液す
る。Further, the prototype battery was stored at 45 ° C. and 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 will deteriorate, but if the electrolyte easily crawls over the negative electrode current collector, electrolysis will occur between the packing and the negative electrode current collector even if the hydrogen gas generation is small. The liquid leaks.
【００２８】これら試験結果を表１に示す。試験結果は
全て２０個の平均値である。また、負極集電体の成形加
工性は、○は加工時に全く問題ないもの、△は希に問題
が発生するもの、×は問題が多発するものである。The results of these tests are shown in Table 1. All test results are average values of 20 pieces. Regarding the moldability of the negative electrode current collector, ◯ indicates that there is no problem during processing, Δ indicates that problems rarely occur, and × indicates that problems frequently occur.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１から明らかなように、ボタン形アルカ
リ電池用の負極ケースを兼ねた負極集電体へのインジウ
ム被覆の厚さは、０．５〜３．５μｍが妥当であり、こ
の範囲より薄い場合は水素ガスの発生の抑制が不十分で
あり、厚い場合は電気特性や放電性能に悪影響を与え、
耐漏液性が悪くなり、さらに負極集電体の成形加工性も
悪化させる。As is clear from Table 1, it is appropriate that the thickness of the indium coating on the negative electrode current collector which also serves as the negative electrode case for the button type alkaline battery is 0.5 to 3.5 μm. When it is thin, the suppression of hydrogen gas generation is insufficient, and when it is thick, it adversely affects the electrical characteristics and discharge performance.
The liquid leakage resistance deteriorates, and the moldability of the negative electrode current collector deteriorates.
【００３１】なお、本発明は上記実施例に限定されるも
のではなく、本発明の範囲を逸脱しない限り、亜鉛合金
粉の変更や他の要素の追加等を行っても差し支えない。
また、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ことは勿
論である。The present invention is not limited to the above embodiments, and zinc alloy powder may be changed or other elements may be added without departing from the scope of the present invention.
Further, although the button type alkaline manganese battery has been described in the above embodiment, the present invention is not limited to this, and can be applied to various button type alkaline batteries having a negative electrode of gel zinc such as a silver oxide battery and an air zinc battery. Of course, it can be applied.
【００３２】[0032]
【発明の効果】以上、説明したように、本発明によって
作成されたボタン形アルカリ電池用負極集電体は、水銀
を添加しないボタン形アルカリ電池に用いても負極集電
体からの水素ガスの発生を抑制できる。また、この負極
集電体を使用し、ゲル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した
本発明のボタン形アルカリ電池は、貯蔵中の漏液や電池
の膨れ、性能劣化等の問題も解消することができる。As described above, the negative electrode current collector for a button type alkaline battery prepared according to the present invention can generate hydrogen gas from the negative electrode current collector even when used in a button type alkaline battery containing no added mercury. Occurrence can be suppressed. Further, using this negative electrode current collector, a button type alkaline battery of the present invention containing an appropriate amount of an indium compound and a surfactant that is stable in an alkaline electrolyte in a gel zinc negative electrode is suitable for leakage during storage and battery Problems such as swelling and performance deterioration can be solved.
【図１】本発明の一実施例であるアルカリマンガン電池
の断面図。FIG. 1 is a cross-sectional view of an alkaline manganese battery which is an embodiment of the present invention.
【図２】図１のＡ部分の詳細図。FIG. 2 is a detailed view of a portion A of 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.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｍ 4/66 Ｈ０１Ｍ 4/66 Ａ (56)参考文献 特開 平５−299093（ＪＰ，Ａ) 特開 平６−65747（ＪＰ，Ａ) 特開 平６−13112（ＪＰ，Ａ) 特開 平５−21056（ＪＰ，Ａ) 特開 昭61−183866（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/64 - 4/84 H01M 6/04 - 6/10 H01M 4/00 - 4/62 H01M 2/02 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI H01M 4/66 H01M 4/66 A (56) Reference JP-A-5-299093 (JP, A) JP-A-6-65747 ( JP, A) JP 6-13112 (JP, A) JP 5-21056 (JP, A) JP 61-183866 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/64-4/84 H01M 6/04-6/10 H01M 4/00-4/62 H01M 2/02
Claims (2)
化剤で構成された水銀無添加の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、負極ケースを兼ねた負
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
分に厚さ０．５〜３．５μｍのインジウムが存在してお
り、かつ水銀無添加の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０．０１〜０．１ｗｔ％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
０．０１ｗｔ％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 zinc alloy powder, alkaline electrolyte, and the button-type alkaline battery having a gel-like zinc negative electrode configurations mercury-free additive in a gelling agent, at least gel-like negative electrode current collector serving also as a negative electrode case There is 0.5-3.5 μm thick indium on the surface that contacts the zinc negative electrode .
And zinc alloy powder in gel-like zinc negative electrode containing no mercury
On the other hand, 0.01 to 0.1 wt% indium as indium
Surfactants that are stable in palladium compounds and alkaline electrolytes
Button containing 0.01 wt% or less
Type alkaline battery .
成形後に負極ケース内面となる側に予めインジウムを電
気メッキした原材料を成形加工したものである請求項１
記載のボタン形アルカリ電池。2. The negative electrode current collector also serving as the negative electrode case,
The raw material, which is obtained by electroplating indium in advance on the side which becomes the negative electrode case inner surface after molding, is molded.
Button type alkaline battery described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576893A JP3522303B2 (en) | 1993-05-27 | 1993-05-27 | Button type alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576893A JP3522303B2 (en) | 1993-05-27 | 1993-05-27 | Button type alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06338327A JPH06338327A (en) | 1994-12-06 |
| JP3522303B2 true JP3522303B2 (en) | 2004-04-26 |
Family
ID=14918357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12576893A Expired - Fee Related JP3522303B2 (en) | 1993-05-27 | 1993-05-27 | Button type alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3522303B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019023010A1 (en) * | 2017-07-24 | 2019-01-31 | Cougeller Research Llc | Rechargeable battery with hydrogen scavenger |
| US11189855B1 (en) | 2020-04-22 | 2021-11-30 | Apple Inc. | Redox mediators as electrolyte additives for alkaline battery cells |
| US11228074B2 (en) | 2017-05-19 | 2022-01-18 | Apple Inc. | Rechargeable battery with anion conducting polymer |
| US11296351B1 (en) | 2018-01-12 | 2022-04-05 | Apple Inc. | Rechargeable battery with pseudo-reference electrode |
| US11367877B1 (en) | 2018-09-19 | 2022-06-21 | Apple Inc. | Aqueous battery current collectors |
| US11817591B2 (en) | 2020-05-22 | 2023-11-14 | Duracell U.S. Operations, Inc. | Seal assembly for a battery cell |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0757717A (en) * | 1993-08-06 | 1995-03-03 | Katayama Tokushu Kogyo Kk | Metallic material plate, negative terminal plate made of the metallic material plate, and manufacture of the terminal plate |
| CN111742429A (en) * | 2018-03-23 | 2020-10-02 | 株式会社村田制作所 | Alkaline battery |
| CN112803109A (en) * | 2021-01-14 | 2021-05-14 | 湖南亿等新能源有限公司 | Soft package button cell |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61183866A (en) * | 1985-02-07 | 1986-08-16 | Yuasa Battery Co Ltd | Alkaline cell |
| JPH0521056A (en) * | 1991-07-10 | 1993-01-29 | Matsushita Electric Ind Co Ltd | Manufacture of zinc alkaline battery |
| US5279905A (en) * | 1992-03-09 | 1994-01-18 | Eveready Battery Company, Inc. | Miniature zinc-air cell having an indium plated anode cupe |
| JPH05299093A (en) * | 1992-04-20 | 1993-11-12 | Matsushita Electric Ind Co Ltd | Button type alkaline battery |
| JPH0665747A (en) * | 1992-08-24 | 1994-03-08 | Okuno Chem Ind Co Ltd | Negative electrode container for alkaline battery |
-
1993
- 1993-05-27 JP JP12576893A patent/JP3522303B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11228074B2 (en) | 2017-05-19 | 2022-01-18 | Apple Inc. | Rechargeable battery with anion conducting polymer |
| US11888112B2 (en) | 2017-05-19 | 2024-01-30 | Apple Inc. | Rechargeable battery with anion conducting polymer |
| WO2019023010A1 (en) * | 2017-07-24 | 2019-01-31 | Cougeller Research Llc | Rechargeable battery with hydrogen scavenger |
| CN110915016A (en) * | 2017-07-24 | 2020-03-24 | 苹果公司 | Rechargeable battery with hydrogen scavenger |
| US11349161B2 (en) | 2017-07-24 | 2022-05-31 | Apple Inc. | Rechargeable battery with hydrogen scavenger |
| US11296351B1 (en) | 2018-01-12 | 2022-04-05 | Apple Inc. | Rechargeable battery with pseudo-reference electrode |
| US11652230B1 (en) | 2018-01-12 | 2023-05-16 | Apple Inc. | Rechargeable battery with pseudo-reference electrode |
| US11367877B1 (en) | 2018-09-19 | 2022-06-21 | Apple Inc. | Aqueous battery current collectors |
| US11189855B1 (en) | 2020-04-22 | 2021-11-30 | Apple Inc. | Redox mediators as electrolyte additives for alkaline battery cells |
| US11817591B2 (en) | 2020-05-22 | 2023-11-14 | Duracell U.S. Operations, Inc. | Seal assembly for a battery cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06338327A (en) | 1994-12-06 |
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