JPH03214563A - Zinc negative electrode for alkaline storage battery - Google Patents
Zinc negative electrode for alkaline storage batteryInfo
- Publication number
- JPH03214563A JPH03214563A JP627290A JP627290A JPH03214563A JP H03214563 A JPH03214563 A JP H03214563A JP 627290 A JP627290 A JP 627290A JP 627290 A JP627290 A JP 627290A JP H03214563 A JPH03214563 A JP H03214563A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- neg
- electrode
- negative electrode
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
《産業上の利用分野》
この発明は、亜鉛または亜鉛合金粉末を用いたアルカリ
電池に関し、特に、水銀の含有量を低下ないしは無水銀
化した場合における亜鉛負極からのガス発生の問題の解
決を図るようにしたアルカリ電池用亜鉛負極に関する。[Detailed Description of the Invention] <<Industrial Application Field>> The present invention relates to alkaline batteries using zinc or zinc alloy powder, and in particular, the present invention relates to alkaline batteries using zinc or zinc alloy powder, and in particular, to reduce the amount of gas emitted from the zinc negative electrode when the mercury content is reduced or mercury-free. This invention relates to a zinc negative electrode for alkaline batteries that attempts to solve the problems that occur.
《従来の技術》
アルカリ電池おいて水素ガスを抑制するための水銀は、
一種の公害物質であるところから、現在では水銀の含有
量を低下させるためのゲル状亜鉛負極の開発が種々なさ
れている。<Prior art> Mercury is used to suppress hydrogen gas in alkaline batteries.
Since mercury is a type of pollutant, various gelled zinc negative electrodes are currently being developed to reduce the content of mercury.
この開発は、一般に、亜鉛に微量金属を添加した亜鉛合
金粉末を作り、この中で特に耐食性の良好な組成の合金
を亜鉛負極材料として採用しているほか、別の開発方向
として界面活性剤などの有機防蝕剤を亜鉛または亜鉛合
金粉末に添加することが行われている。This development generally involves making zinc alloy powder by adding trace metals to zinc, and among these, alloys with particularly good corrosion resistance are used as zinc negative electrode materials. Organic corrosion inhibitors have been added to zinc or zinc alloy powders.
本発明は、後者の有機防蝕剤を添加することによって低
水銀ないしは無水銀化に伴う亜鉛の腐蝕を防止するもの
である。The present invention prevents corrosion of zinc due to low or no mercury by adding the latter organic corrosion inhibitor.
この種の腐蝕防止剤としては、従来、例えば、特公昭５
２−７８１０号公報に示すようにポリオキシエチレンア
ルキルエーテルや、特開昭６１−２７０６３号公報に示
すようにバーフルオロ有機化合物を用いた防蝕技術が提
案されている。Conventionally, as this type of corrosion inhibitor, for example,
Corrosion prevention techniques using polyoxyethylene alkyl ether as shown in Japanese Patent Application No. 2-7810 and barfluoro organic compounds as shown in Japanese Patent Application Laid-Open No. 61-27063 have been proposed.
これらの技術は、いずれも亜鉛の表面に強力な吸着層を
形成することで腐蝕を防止し、また、これによって水素
ガスの発生を抑制することに主眼をおいている。All of these techniques focus on preventing corrosion by forming a strong adsorption layer on the surface of zinc, and thereby suppressing the generation of hydrogen gas.
《課題を解決するための手段》
しかし、実際にはこれらの防蝕剤を添加した場合であっ
ても顕著な防蝕効果は認められず、水銀量の低減のため
の有効な手段とはなっていなかった。《Means for solving the problem》 However, in reality, even when these anticorrosive agents are added, no significant anticorrosion effect is observed, and they are not an effective means for reducing the amount of mercury. Ta.
つまり、これらの界面活性剤はいずれも十分な吸着層を
亜鉛表面に形成するには至っておらず、いずれもが求化
度１．０％以下に対する有効な手段とはなっていなかっ
た。In other words, none of these surfactants was able to form a sufficient adsorption layer on the zinc surface, and none of them were effective means for reducing the degree of attraction to 1.0% or less.
なお、ポリオキシエチレンアルキルエーテルは、初期状
態では防蝕性があることが認められるものの、長期保存
によって防蝕効果が低減していた。It should be noted that although polyoxyethylene alkyl ether was recognized to have anti-corrosion properties in its initial state, the anti-corrosion effect was reduced by long-term storage.
そこで本発明者らは、ポリオキシエチレンアルキルエー
テルの安定化を図るべく種々検討した結果、これとポリ
オキシエチレンアルキルアマイドとの混合物が、氷化度
１％以下の低氷化状態における水素ガス発生抑制効果を
十分に得ることを確認した。As a result of various studies aimed at stabilizing polyoxyethylene alkyl ether, the present inventors found that a mixture of polyoxyethylene alkyl ether and polyoxyethylene alkyl ether can generate hydrogen gas in a low freezing state with a degree of freezing of 1% or less. It was confirmed that a sufficient suppressive effect could be obtained.
本発明は以上の知得に基づきなされたもので、その目的
とするところは、亜鉛またはその合金粉末に対する永化
度が１％以下であっても充分にガス発生抑制効果が得ら
れるアルカリ電池用亜鉛負極を提供するものである。The present invention has been made based on the above knowledge, and its purpose is to provide an alkaline battery that can sufficiently suppress gas generation even if the permanence of zinc or its alloy powder is 1% or less. It provides a zinc negative electrode.
《課題を解決するための手段》
前記目的を達成するため、この発明のアルカリ電池は、
亜鉛ないし亜鉛合金粉末に組成割合が重量比で２０ ：
８０〜８０ ： ２０の非イオン系のポリオキシエチ
レンアルキルエステルと、ポリオキシエチレンアルキル
アマイドを混合した状態で添加した亜鉛負極を用いたも
のである。<Means for Solving the Problems> In order to achieve the above object, the alkaline battery of the present invention has the following features:
The composition ratio of zinc or zinc alloy powder is 20% by weight:
80-80: A zinc negative electrode containing a mixture of 20 nonionic polyoxyethylene alkyl ester and polyoxyethylene alkyl amide was used.
前記組成割合が２０ ： ８０〜８０ ： ２０の範囲
内の場合には、長期安定性に富み、耐食性が向上するが
、この場合を越えた場合には、長期安定性が低下し、長
期保存後の耐食性が劣るので、以上の組成割合で亜鉛ま
たはその合金粉に添加することが必要である。When the composition ratio is within the range of 20:80 to 80:20, long-term stability is high and corrosion resistance is improved; however, when it exceeds this range, long-term stability decreases and after long-term storage. Since the corrosion resistance of zinc is poor, it is necessary to add it to zinc or its alloy powder in the above composition ratio.
以上の非イオン界面活性剤の亜鉛負極に対する添加量は
、ゲル状亜鉛負極中の亜鉛または亜鉛合金粉末に対して
１０〜１ ０ ０ １）Ｉ）Ｉ１の範囲とすることが望
ましく、前記数値を下回った場合には絶対量不足により
亜鉛の耐食性が低下する。The amount of the nonionic surfactant added to the zinc negative electrode is desirably in the range of 10 to 100 1)I) to the zinc or zinc alloy powder in the gelled zinc negative electrode, and the above value is If it is less than that, the corrosion resistance of zinc will decrease due to absolute deficiency.
また、その逆に前記数値を越えた添加量では吸着層の厚
みが厚すぎることにより、放電性能の低下を招来する。On the other hand, if the amount added exceeds the above-mentioned value, the thickness of the adsorption layer becomes too thick, resulting in a decrease in discharge performance.
したがって、前記数値の範囲内の添加が望ましく、２０
〜５ ０ ｐｐｍの範囲がより好ましい結果を与える。Therefore, it is desirable to add within the range of the above numerical value, and 20
A range of 50 ppm gives more favorable results.
なお、本発明では亜鉛単体のほか、亜鉛合金粉末を使用
するが、この亜鉛合金粉末としては、亜鉛にＰｂ，Ｂ１
，ＡＩ ，Ｉｎ．Ｇａ，Ｍｇのうちの１種以上を微量
含有したものを選択すればよく、低永化材料として好ま
しい組成とすれば良い。In addition, in the present invention, zinc alloy powder is used in addition to zinc alone, and this zinc alloy powder includes zinc with Pb, B1
, AI, In. It is sufficient to select a material containing a trace amount of one or more of Ga and Mg, and the composition may be preferable as a low aging material.
《作 用》
以上の組成の有機耐蝕剤を微量添加した亜鉛負極は、無
添加あるいは単独添加のものに比べて水銀含有量１％以
下で長期間に亘ってガス発生抑制効果を得ることができ
、また、添加量を適宜に調整することで、放電性能に対
する悪影響を防止できる。《Function》 A zinc negative electrode to which a small amount of an organic anticorrosion agent having the above composition has been added can have a gas generation suppressing effect for a long period of time with a mercury content of 1% or less, compared to one without additives or with only one additive added. Moreover, by appropriately adjusting the amount added, an adverse effect on discharge performance can be prevented.
《発明の効果》
以上の構成によれば、従来の有機防蝕剤単独を用いたも
のに比べて水銀量を低減したとしても亜鉛゛の腐蝕に対
する抑制効果があり、水銀量を効果的に低減でき、しか
も放電性能の低下もないので、低水銀化ないしは無水銀
化を達成する上で有用である。<<Effects of the Invention>> According to the above configuration, even if the amount of mercury is reduced compared to the case where a conventional organic corrosion inhibitor is used alone, there is an effect of suppressing corrosion of zinc, and the amount of mercury can be effectively reduced. Moreover, since there is no deterioration in discharge performance, it is useful in achieving low or no mercury.
《実 施 例》 以下好ましい実施例につき詳細に説明する。"Example" Preferred embodiments will be described in detail below.
但し本発明は以下の実施例に限定されるものではない。However, the present invention is not limited to the following examples.
水銀量０．１％に設定した以下の組成のゲル状負極亜鉛
を作成し、これに表のＮｏ３〜Ｎｏ６の組成比の非イオ
ン系のポリオキシエチレンアルキルエステルと、ポリオ
キシエチレンアルキルアマイドを混合した状態で亜鉛に
対して２ ０ ｐｐｍ添加し、６０℃の温度雰囲気下で
ガス発生試験を実施し、以下の表１のごとき結果が得ら
れた。A gelled negative electrode zinc with the following composition was prepared with a mercury content of 0.1%, and nonionic polyoxyethylene alkyl ester and polyoxyethylene alkyl amide having the composition ratios No. 3 to No. 6 in the table were mixed therewith. In this state, 20 ppm of zinc was added, and a gas generation test was conducted in an atmosphere at a temperature of 60° C., and the results shown in Table 1 below were obtained.
なお、比較例として従来の１．５％Ｈｇを含むゲル状亜
鉛負極を用いたもの（Ｎｏ ９） 、各成分単独のもの
（Ｎｏ １．８）、 本発明の範囲を逸脱した組成比の
もの（Ｎｏ ２．７）を掲げた。Comparative examples include one using a conventional gelled zinc negative electrode containing 1.5% Hg (No. 9), one using each component alone (No. 1.8), and one using a composition ratio outside the scope of the present invention. (No. 2.7) was raised.
また、ゲル状亜鉛負極の組成は以下の通りである。The composition of the gelled zinc negative electrode is as follows.
０．１％氷化亜鉛合金粉末６０ｗｔ％＊４（ｌｔ％ＫＯ
Ｈ ３８％
ゲル化剤 ２％
合計 １００％
また、亜鉛合金粉末の組成は亜鉛に対して５００ｐｐＩ
ｌｐｂ − ６ ０ ０ｐｐｍ ＡΩ−２００ｐｐＩＩ
Ｉｎを添加した合金である。0.1% iced zinc alloy powder 60wt%*4 (lt%KO
H 38% Gelling agent 2% Total 100% Also, the composition of the zinc alloy powder is 500 ppI to zinc.
lpb-600ppm AΩ-200ppII
This is an alloy containing In.
表
＊但しＡ−ポリオキシエチレンアルキルエステルＢ−ポ
リオキシエチレンアルキルアマイド以上の表に示す結果
から、本発明の組成比の範囲ではその水銀量が０６ １
％と極めて少量であるにも係わらず、従来例の水銀量１
．５％より上回るガス発生抑制効果を示した。Table *However, A-Polyoxyethylene alkyl ester B-Polyoxyethylene alkyl amide From the results shown in the above table, within the composition ratio range of the present invention, the amount of mercury is 0.6 1
Although the amount of mercury is extremely small at 1%, the amount of mercury in the conventional example is
．． It showed a gas generation suppressing effect exceeding 5%.
これに対し、それぞの単独あるいは本発明の範囲を逸脱
した組成比では、初期状態のガス発生抑止効果はあるも
のの、３０日保存状態ではいずれも従来例を上回るガス
発生量であり、長期保存により抑制効果が低下すること
を示した。On the other hand, each of these alone or with a composition ratio outside the range of the present invention has the effect of suppressing gas generation in the initial state, but after 30 days of storage, the amount of gas generated exceeds that of the conventional example. It was shown that the inhibitory effect was decreased by
Claims (1)
０：８０〜８０：２０の非イオン系のポリオキシエチレ
ンアルキルエステルと、ポリオキシエチレンアルキルア
マイドとを混合した状態で添加した亜鉛負極を用いるこ
とを特徴とするアルカリ電池用亜鉛負極。(1) The composition ratio of zinc or zinc alloy powder is 2 by weight.
A zinc negative electrode for an alkaline battery characterized by using a zinc negative electrode to which a mixture of nonionic polyoxyethylene alkyl ester and polyoxyethylene alkyl amide is added in a ratio of 0:80 to 80:20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP627290A JP2796154B2 (en) | 1990-01-17 | 1990-01-17 | Zinc negative electrode for alkaline batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP627290A JP2796154B2 (en) | 1990-01-17 | 1990-01-17 | Zinc negative electrode for alkaline batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03214563A true JPH03214563A (en) | 1991-09-19 |
| JP2796154B2 JP2796154B2 (en) | 1998-09-10 |
Family
ID=11633784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP627290A Expired - Fee Related JP2796154B2 (en) | 1990-01-17 | 1990-01-17 | Zinc negative electrode for alkaline batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796154B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
-
1990
- 1990-01-17 JP JP627290A patent/JP2796154B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2796154B2 (en) | 1998-09-10 |
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