JPH05314968A - Alkaline battery - Google Patents
Alkaline batteryInfo
- Publication number
- JPH05314968A JPH05314968A JP11884392A JP11884392A JPH05314968A JP H05314968 A JPH05314968 A JP H05314968A JP 11884392 A JP11884392 A JP 11884392A JP 11884392 A JP11884392 A JP 11884392A JP H05314968 A JPH05314968 A JP H05314968A
- Authority
- JP
- Japan
- Prior art keywords
- indium
- zinc alloy
- alloy powder
- added
- trioxide
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Detergent Compositions (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有水銀アルカリ電池と
同等の性能を有する無水銀化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 mercury-free alkaline battery having the same performance as a mercury-containing alkaline battery.
【０００２】[0002]
【従来の技術】従来、無水銀化アルカリ電池において
は、防食効果を高めるため、耐食性亜鉛合金に無機又は
有機インヒビターをゲル状負極に添加していた。2. Description of the Related Art Conventionally, in a mercury-free alkaline battery, an inorganic or organic inhibitor has been added to a gelled negative electrode in a corrosion resistant zinc alloy in order to enhance the anticorrosion effect.
【０００３】[0003]
【発明が解決しようとする課題】しかし、無機インヒビ
ターを添加した場合には、未放電の防食効果は不十分と
なり、また有機インヒビターを添加した場合には、部分
放電後の防食効果が殆どみられず、特に有機インヒビタ
ーを多量に添加すると、放電性能に悪影響を及ぼす不都
合があった。However, when an inorganic inhibitor is added, the anti-corrosion effect before undischarge becomes insufficient, and when an organic inhibitor is added, the anti-corrosion effect after partial discharge is almost observed. However, when a large amount of organic inhibitor is added, there is a disadvantage that discharge performance is adversely affected.
【０００４】本発明は、上記事情に鑑み、環境保全上の
問題がある水銀を用いることなく十分な防食効果を発揮
し得るアルカリ電池を提供することを目的とする。In view of the above circumstances, an object of the present invention is to provide an alkaline battery which can exhibit a sufficient anticorrosion effect without using mercury, which has a problem in environmental protection.
【０００５】[0005]
【課題を解決するための手段】本発明によるアルカリ電
池は、亜鉛合金粉末と、アルカリ電解液及びゲル化剤か
らなるゲル状負極とに、三酸化二インジウム（Ｉｎ2 Ｏ
3 ）又は水酸化インジウム（Ｉｎ（ＯＨ）3 ）及びアル
キルアマイド酸化エチレン縮合物型の非イオン界面活性
剤を添加して構成される。The alkaline battery according to the present invention comprises a zinc alloy powder, a gelled negative electrode composed of an alkaline electrolyte and a gelling agent, and indium trioxide (In 2 O 3).
3 ) or indium hydroxide (In (OH) 3 ) and an alkyl amide ethylene oxide condensate type nonionic surfactant are added.
【０００６】また、上記三酸化二インジウム又は水酸化
インジウムの上記亜鉛合金粉末に対する添加率をインジ
ウム換算量で１００〜１０００ppm とし、上記アルキル
アマイド酸化エチレン縮合物型の非イオン界面活性剤の
上記亜鉛合金粉末に対する添加率を５〜１００ppm とし
て構成される。Further, the addition ratio of the indium trioxide or indium hydroxide to the zinc alloy powder is 100 to 1000 ppm in terms of indium, and the zinc alloy of the alkyl amide ethylene oxide condensate type nonionic surfactant is used. The powder is added in an amount of 5 to 100 ppm.
【０００７】[0007]
【作用】上記した構成により、本発明は、三酸化二イン
ジウム又は水酸化インジウムとアルキルアマイド酸化エ
チレン縮合物型の非イオン界面活性剤との相互作用によ
り、防食作用が高められ、水素ガスの発生が抑制される
ように作用する。With the above-mentioned constitution, the present invention enhances the anticorrosion action by the interaction between the indium trioxide or indium hydroxide and the alkyl amide ethylene oxide condensate type nonionic surfactant, and the generation of hydrogen gas. Acts to be suppressed.
【０００８】[0008]
【実施例】以下、本発明の実施例について説明する。EXAMPLES Examples of the present invention will be described below.
【０００９】亜鉛合金粉末（鉛を５００ppm 含有するも
の）６３％と、水酸化カリウム（４０％ＫＯＨ）３５％
と、ゲル化剤２％とからなるゲル状負極に、三酸化二イ
ンジウム（Ｉｎ2 Ｏ3 ）及び非イオン界面活性剤を添加
して、アルカリ電池を製造した。この際、非イオン界面
活性剤としては、アルキルアマイド酸化エチレン縮合物
型その他の各種の非イオン界面活性剤を用いた。63% zinc alloy powder (containing 500 ppm lead) and 35% potassium hydroxide (40% KOH)
And indium trioxide (In 2 O 3 ) and a nonionic surfactant were added to a gelled negative electrode composed of 1% and a gelling agent of 2% to manufacture an alkaline battery. At this time, alkyl amide ethylene oxide condensate type and various other nonionic surfactants were used as the nonionic surfactant.
【００１０】各非イオン界面活性剤を亜鉛合金粉末に対
して２０ppm 添加したアルカリ電池について、三酸化二
インジウムの添加の有無が水素ガスの発生量に及ぼす影
響を調べるため、三酸化二インジウムを亜鉛合金粉末に
対してインジウム換算量で１００ppm 添加した場合と、
三酸化二インジウムを添加しない場合におけるガス発生
量をそれぞれ測定した。ガス発生量の測定は、図１に示
すようなガス発生装置を用いて行なった。即ち、フラス
コ１内にゲル状負極２を入れ、その上に流動パラフィン
３を充填し、その状態のまま６０℃で１０日間静置した
後、流動パラフィン３の上面の上昇量を目盛り付きピペ
ット５で読み取り、ガス発生量を算出した。その結果を
表１に示す。In an alkaline battery in which each nonionic surfactant was added to the zinc alloy powder in an amount of 20 ppm, in order to investigate the effect of the addition or non-addition of diindium trioxide on the amount of hydrogen gas produced, zinc indium trioxide was added. In the case of adding 100 ppm in terms of indium to the alloy powder,
The amount of gas generated when no indium trioxide was added was measured. The amount of gas generated was measured using a gas generator as shown in FIG. That is, the gelled negative electrode 2 was placed in the flask 1, the liquid paraffin 3 was filled therein, and the liquid paraffin 3 was left still at 60 ° C. for 10 days. And the gas generation amount was calculated. The results are shown in Table 1.
【００１１】 表１から明らかなように、４種類の非イオン界面活性剤
の全てについて、三酸化二インジウムの添加によって水
素ガスの発生が抑制された結果となっている。即ち、三
酸化二インジウムを添加しない場合には順に１０８、１
３３、９７及び１１１μｌ／ｇであったガス発生量が、
三酸化二インジウムの添加によってそれぞれ５２、１０
５、９２及び１０６μｌ／ｇに減少し、特にアルキルア
マイド酸化エチレン縮合物型の非イオン界面活性剤につ
いては半分以下に減少しており、ガス発生が大幅に抑制
されていることが分かる。[0011] As is clear from Table 1, generation of hydrogen gas was suppressed by the addition of diindium trioxide for all four types of nonionic surfactants. That is, when no indium trioxide is added, 108 and 1
The amount of gas generated was 33, 97 and 111 μl / g,
52,10 by addition of indium trioxide respectively
5, 92 and 106 μl / g, especially for alkyl amide ethylene oxide condensate type nonionic surfactants, the amount was reduced to less than half, and it can be seen that gas generation is significantly suppressed.
【００１２】また、このアルキルアマイド酸化エチレン
縮合物型の非イオン界面活性剤について、非イオン界面
活性剤の添加率を一定（２０ ppm／Ｚｎ）とし、三酸化
二インジウムの添加率を０〜３０００ ppm／Ｚｎの範囲
内で変えた場合に、ガス発生量がどのように変化するか
を調べた。その結果を表２に示す。Regarding the alkyl amide ethylene oxide condensate type nonionic surfactant, the addition ratio of the nonionic surfactant is constant (20 ppm / Zn), and the addition ratio of diindium trioxide is 0 to 3000. It was investigated how the gas generation amount changed when the amount was changed within the range of ppm / Zn. The results are shown in Table 2.
【００１３】 表２から明らかなように、三酸化二インジウムを亜鉛合
金粉末に対してインジウム換算量で１００、３００又は
１０００ppm 添加したときに、ガス発生量がピーク的に
少なくなっており、これより多くても少なくても抑制効
果が薄れていることが分かる。なお、一般に、ガス発生
量が約１００μｌ／ｇを越えると漏液しやすくなると言
われているが、三酸化二インジウムを１００、３００、
１０００ppm 添加した場合には、ガス発生量がそれぞれ
５２、４９、７８μｌ／ｇであり、いずれも１００μｌ
／ｇを下回っているので、漏液の危険性は極めて少ない
こととなる。[0013] As is clear from Table 2, when indium trioxide is added to the zinc alloy powder in an amount of 100, 300 or 1000 ppm in terms of indium, the gas generation amount is reduced to a peak, and even if it is more than this amount. It can be seen that the suppression effect is weakened at least. It is generally said that when the gas generation amount exceeds about 100 μl / g, liquid leakage is likely to occur.
When 1000ppm was added, the amount of gas generated was 52, 49 and 78μl / g, respectively, 100μl
Since it is less than / g, the risk of liquid leakage is extremely small.
【００１４】逆に、このアルキルアマイド酸化エチレン
縮合物型の非イオン界面活性剤について、三酸化二イン
ジウムの添加率を一定（１００ ppm／Ｚｎ）とし、非イ
オン界面活性剤の添加率を０〜５００ ppm／Ｚｎの範囲
内で変えた場合に、ガス発生量及び低温時の放電性能
（−１０℃で１０Ω連続、終止電圧０．９Ｖ）がどのよ
うに変化するかを調べた。同様にして、０．１５％の水
銀を添加して製造した従来のアルカリ電池についても、
ガス発生量及び低温時の放電性能を測定した。その結果
をまとめて表３に示す。On the contrary, with respect to the alkyl amide ethylene oxide condensate type nonionic surfactant, the addition ratio of diindium trioxide is constant (100 ppm / Zn), and the addition ratio of the nonionic surfactant is 0 to 0. It was examined how the amount of gas generated and the discharge performance at low temperature (10Ω continuous at -10 ° C, final voltage 0.9V) changed when the amount was changed within the range of 500 ppm / Zn. Similarly, for a conventional alkaline battery manufactured by adding 0.15% mercury,
The gas generation amount and the discharge performance at low temperature were measured. The results are summarized in Table 3.
【００１５】 ガス発生量に関しては、表３から明らかなように、非イ
オン界面活性剤の添加率が高い程、ガス発生量が少な
く、非イオン界面活性剤を５ ppm／Ｚｎ以上添加した場
合には、ガス発生量が１００μｌ／ｇ未満となり、漏液
の危険性は極めて少ない。また、非イオン界面活性剤を
５〜２０ ppm／Ｚｎ添加すれば、有水銀アルカリ電池と
同程度のガス発生抑制効果が得られることが分かる。[0015] Regarding the gas generation amount, as is clear from Table 3, the higher the addition rate of the nonionic surfactant is, the smaller the gas generation amount is. When the nonionic surfactant is added at 5 ppm / Zn or more, the gas generation amount is The generated amount is less than 100 μl / g, and the risk of liquid leakage is extremely low. Further, it is understood that when the nonionic surfactant is added in an amount of 5 to 20 ppm / Zn, the same gas generation suppressing effect as that of the mercury-containing alkaline battery can be obtained.
【００１６】一方、低温時の放電性能に関しては、表３
に示すように、非イオン界面活性剤の添加率が高い程、
放電時間が短縮される傾向にあるが、非イオン界面活性
剤の添加率が１００ ppm／Ｚｎ以下の場合は、有水銀ア
ルカリ電池と比べて遜色のない低温放電性能を有してい
る。On the other hand, Table 3 shows the discharge performance at low temperature.
As shown in, the higher the nonionic surfactant addition rate,
Although the discharge time tends to be shortened, when the addition rate of the nonionic surfactant is 100 ppm / Zn or less, it has low-temperature discharge performance comparable to that of the mercury-containing alkaline battery.
【００１７】更に、アルキルアマイド酸化エチレン縮合
物型の非イオン界面活性剤について、部分放電（３．９
Ω×２Ｈ）後の耐漏液性能を調べるため、非イオン界面
活性剤の添加率を一定（２０ ppm／Ｚｎ）とし、三酸化
二インジウムの添加率を０〜３０００ ppm／Ｚｎの範囲
内で変えたアルカリ電池を２０本ずつ製造し、温度６０
℃、相対湿度９０％の条件下で４０日間放置し、１０
日、２０日及び４０日経過時の漏液数をチェックした。
その結果を表４に示す。Furthermore, regarding the alkyl amide ethylene oxide condensate type nonionic surfactant, partial discharge (3.9
In order to investigate the leakage resistance after Ω × 2H), the addition rate of the nonionic surfactant was fixed (20 ppm / Zn), and the addition rate of diindium trioxide was changed within the range of 0 to 3000 ppm / Zn. 20 alkaline batteries are manufactured at a temperature of 60
Leave for 40 days under the conditions of ℃ and 90% relative humidity for 10 days.
The number of leaks at day, 20th and 40th day was checked.
The results are shown in Table 4.
【００１８】 表４から明らかなように、特に三酸化二インジウムを亜
鉛合金粉末に対してインジウム換算量で１００〜１００
０ppm 添加したときに、部分放電後の耐漏液性能が優れ
ていることが分かる。即ち、三酸化二インジウムの添加
率がゼロである場合には、２０本の試験体のうち３本
（即ち、１５％）が１０日経過時までに漏液し、８本
（即ち、４０％）が２０日経過時までに漏液し、１８本
（即ち、９０％）が４０日経過時までに漏液した。これ
に対して、三酸化二インジウムの添加率が３０ ppm／Ｚ
ｎである場合には、２０日経過時までに漏液したものは
１本もなく、４０日経過時までに２０本の試験体のうち
５本（即ち、２５％）が漏液したに過ぎない。また、三
酸化二インジウムの添加率が１００、３００又は１００
０ ppm／Ｚｎである場合には、４０日経過時までに漏液
したものは１本もなかった。更に、三酸化二インジウム
の添加率が３０００ ppm／Ｚｎである場合には、１０日
経過時までに漏液したものは１本もなく、２０日経過時
までに２０本の試験体のうち２本（即ち、１０％）が漏
液し、４０日経過時までに３本（即ち、１５％）が漏液
したに過ぎない。[0018] As is clear from Table 4, indium trioxide is 100 to 100 in terms of indium in terms of zinc alloy powder.
It can be seen that the liquid leakage resistance after partial discharge is excellent when 0 ppm is added. That is, when the addition rate of diindium trioxide is zero, 3 out of 20 test bodies (that is, 15%) leaked by 10 days, and 8 (that is, 40%). ) Leaked by 20 days, and 18 (ie, 90%) leaked by 40 days. On the other hand, the addition rate of indium trioxide is 30 ppm / Z
In the case of n, none of the samples leaked by the time of 20 days, and only 5 (that is, 25%) of the 20 test samples leaked by the time of 40 days. Absent. Further, the addition ratio of diindium trioxide is 100, 300 or 100.
In the case of 0 ppm / Zn, none of the liquid leaked by 40 days. Furthermore, when the addition rate of diindium trioxide was 3000 ppm / Zn, no one leaked by the time of 10 days, and 2 out of 20 test bodies by the time of 20 days. Only 3 bottles (ie 15%) were leaked by 40 days (ie 10%).
【００１９】なお、上述の実施例においては、三酸化二
インジウム（Ｉｎ2 Ｏ3 ）を添加した場合について説明
したが、三酸化二インジウムの代わりに水酸化インジウ
ム（Ｉｎ（ＯＨ）3 ）を添加することも可能である。In the above-mentioned embodiments, the case where diindium trioxide (In 2 O 3 ) is added has been described, but indium hydroxide (In (OH) 3 ) is added instead of diindium trioxide. It is also possible to do so.
【００２０】[0020]
【発明の効果】以上説明したように、本発明によれば、
亜鉛合金粉末、水酸化カリウム等のアルカリ電解液及び
ゲル化剤からなるゲル状負極に、三酸化二インジウム
（Ｉｎ2 Ｏ3 ）又は水酸化インジウム（Ｉｎ（Ｏ
Ｈ）3 ）及びアルキルアマイド酸化エチレン縮合物型の
非イオン界面活性剤を添加して構成したので、三酸化二
インジウム又は水酸化インジウムとアルキルアマイド酸
化エチレン縮合物型の非イオン界面活性剤との相互作用
により、防食作用が高められ、水素ガスの発生が抑制さ
れることから、環境保全上の問題がある水銀を用いるこ
となく十分な防食効果を発揮し得るアルカリ電池を提供
することが可能となる。As described above, according to the present invention,
Didium indium trioxide (In 2 O 3 ) or indium hydroxide (In (O) was added to a gelled negative electrode composed of zinc alloy powder, an alkaline electrolyte such as potassium hydroxide, and a gelling agent.
H) 3 ) and an alkyl amide ethylene oxide condensate type nonionic surfactant are added, so that the indium trioxide or indium hydroxide and the alkyl amide ethylene oxide condensate type nonionic surfactant are Since the anticorrosion effect is enhanced by the interaction and the generation of hydrogen gas is suppressed, it is possible to provide an alkaline battery that can exhibit a sufficient anticorrosion effect without using mercury, which has a problem in environmental protection. Become.
【００２１】また、上記三酸化二インジウム又は水酸化
インジウムの上記亜鉛合金粉末に対する添加率をインジ
ウム換算量で１００〜１０００ppm とし、上記アルキル
アマイド酸化エチレン縮合物型の非イオン界面活性剤の
上記亜鉛合金粉末に対する添加率を５〜１００ppm とし
て構成すると、上述の効果を顕著なものとすることが出
来る。The addition ratio of the indium trioxide or indium hydroxide to the zinc alloy powder is 100 to 1000 ppm in terms of indium, and the zinc alloy of the alkyl amide ethylene oxide condensate type nonionic surfactant is used. When the addition rate to the powder is set to 5 to 100 ppm, the above effects can be made remarkable.
【図１】ガス発生装置の正断面図である。FIG. 1 is a front sectional view of a gas generator.
１……フラスコ ２……ゲル状負極 ３……流動パラフィン ５……目盛り付きピペット 1 ... Flask 2 ... Gel negative electrode 3 ... Liquid paraffin 5 ... Scaled pipette
───────────────────────────────────────────────────── フロントページの続き (72)発明者 都築 秀典 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hidenori Tsuzuki, 5-36-11 Shinbashi, Minato-ku, Tokyo Inside Fuji Electric Chemical Co., Ltd.
Claims (2)
化剤からなるゲル状負極に、三酸化二インジウム又は水
酸化インジウム及びアルキルアマイド酸化エチレン縮合
物型の非イオン界面活性剤 を添加したことを特徴とするアルカリ電池。1. A non-ionic surfactant of diindium trioxide or indium hydroxide and an alkyl amide ethylene oxide condensate type is applied to a gelled negative electrode comprising zinc alloy powder, an alkaline electrolyte and a gelling agent. Alkaline battery characterized by the addition of.
ムの亜鉛合金粉末に対する添加率をインジウム換算量で
１００〜１０００ppm とし、アルキルアマイド酸化エチ
レン縮合物型の非イオン界面活性剤の亜鉛合金粉末に対
する添加率を５〜１００ppm として構成した請求項１記
載のアルカリ電池。2. The addition ratio of indium trioxide or indium hydroxide to the zinc alloy powder is 100 to 1000 ppm in terms of indium, and the addition ratio of the alkyl amide ethylene oxide condensate type nonionic surfactant to the zinc alloy powder. The alkaline battery according to claim 1, wherein the content is 5 to 100 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11884392A JP3293164B2 (en) | 1992-05-12 | 1992-05-12 | Alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11884392A JP3293164B2 (en) | 1992-05-12 | 1992-05-12 | Alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05314968A true JPH05314968A (en) | 1993-11-26 |
| JP3293164B2 JP3293164B2 (en) | 2002-06-17 |
Family
ID=14746532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11884392A Expired - Fee Related JP3293164B2 (en) | 1992-05-12 | 1992-05-12 | Alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3293164B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947422A (en) * | 2010-08-24 | 2011-01-19 | 天津大学 | Alkaline solution gel and preparation method as well as application thereof |
-
1992
- 1992-05-12 JP JP11884392A patent/JP3293164B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947422A (en) * | 2010-08-24 | 2011-01-19 | 天津大学 | Alkaline solution gel and preparation method as well as application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3293164B2 (en) | 2002-06-17 |
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