JP2739363B2 - Manganese dry cell - Google Patents

Manganese dry cell

Info

Publication number
JP2739363B2
JP2739363B2 JP30669689A JP30669689A JP2739363B2 JP 2739363 B2 JP2739363 B2 JP 2739363B2 JP 30669689 A JP30669689 A JP 30669689A JP 30669689 A JP30669689 A JP 30669689A JP 2739363 B2 JP2739363 B2 JP 2739363B2
Authority
JP
Japan
Prior art keywords
zinc
manganese dry
mercury
cationic surfactant
electrolytic solution
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 - Lifetime
Application number
JP30669689A
Other languages
Japanese (ja)
Other versions
JPH03167757A (en
Inventor
幸次郎 宮坂
深雪 満田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FDK Twicell Co Ltd
Original Assignee
Toshiba Battery Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Battery Co Ltd filed Critical Toshiba Battery Co Ltd
Priority to JP30669689A priority Critical patent/JP2739363B2/en
Publication of JPH03167757A publication Critical patent/JPH03167757A/en
Application granted granted Critical
Publication of JP2739363B2 publication Critical patent/JP2739363B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • Y02E60/12

Landscapes

  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Primary Cells (AREA)

Description

【発明の詳細な説明】 〔発明の目的〕 (産業上の利用分野) 本発明はマンガン乾電池の負極亜鉛または亜鉛合金の
腐食抑制に関するものである。
DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to the inhibition of corrosion of a negative electrode zinc or zinc alloy of a manganese dry battery.

(従来の技術) 一般にマンガン乾電池の負極材として、化学的に比較
的安定で加工性に富み安価であることから、鉛、カドミ
ウム等を少量添加した亜鉛缶が使用されている。しか
し、そのまま使用すると亜鉛の腐食が激しく、長期保存
後の電池は性能劣化が起き易くなる。従って通常のマン
ガン乾電池には、亜鉛缶の有効面積当り0.01〜0.2mg/cm
2程度の水銀が添加されている。
(Prior Art) As a negative electrode material of a manganese dry battery, a zinc can to which a small amount of lead, cadmium or the like is added is generally used because it is relatively stable chemically, has good workability and is inexpensive. However, if it is used as it is, the corrosion of zinc is severe, and the battery after long-term storage tends to deteriorate in performance. Therefore, for a normal manganese dry battery, 0.01 to 0.2 mg / cm per effective area of the zinc can
About 2 mercury is added.

(発明が解決しようとする課題) しかし、この程度の量の水銀を含有するマンガン乾電
池は、廃棄されても環境汚染は起こらないとされている
が、これからの社会環境ではより安全な水銀無添加また
は水銀低減化マンガン乾電池が必要となり、亜鉛の防食
技術の確立が不可欠となっている。
(Problems to be solved by the invention) However, manganese batteries containing this amount of mercury are said to not cause environmental pollution even if they are disposed of. However, in a future social environment, it is safer to add no mercury. Alternatively, a mercury-reduced manganese dry battery is required, and it is indispensable to establish a technique for preventing corrosion of zinc.

本発明は前述の問題を解決するためになされたもの
で、負極として用いられる亜鉛または亜鉛合金の腐食を
極力抑えたマンガン乾電池を提供することを目的とす
る。
The present invention has been made to solve the above-described problem, and has as its object to provide a manganese dry battery in which corrosion of zinc or a zinc alloy used as a negative electrode is suppressed as much as possible.

[発明の構成] (課題を解決するための手段) 本発明者は前述の目的を達成するため鋭意研究したと
ころ、電解液等に炭素数12のアルキル基が、含有アルキ
ル基の90基数%以上であるカチオン界面活性剤モノアル
キル第四級アンモニウムクロライドを特定量添加するこ
とにより、正極の二酸化マンガンの電位を劣化させるこ
となく、亜鉛の腐食を極力抑えることを見い出し、本発
明に至った。
[Constitution of the Invention] (Means for Solving the Problems) The present inventor has conducted intensive studies in order to achieve the above-mentioned object. By adding a specific amount of the cationic surfactant monoalkyl quaternary ammonium chloride, it was found that the corrosion of zinc was suppressed as much as possible without deteriorating the potential of manganese dioxide of the positive electrode, and the present invention was reached.

すなわち、本発明は塩化亜鉛溶液及び/または塩化ア
ンモニウム溶液を主成分とする電解液を用いるマンガン
乾電池において、電池内に該カチオン界面活性剤を電解
液に対して、0.002〜0.2容積%存在させたことを特徴と
するマンガン乾電池である。
That is, in the present invention, in a manganese dry battery using an electrolytic solution containing a zinc chloride solution and / or an ammonium chloride solution as a main component, the cationic surfactant is present in the battery in an amount of 0.002 to 0.2% by volume based on the electrolytic solution. A manganese dry battery characterized in that:

該カチオン界面活性剤の添加範囲については、電解液
に対して0.002〜0.2容積%が好ましく、0.002容積%よ
り少ない場合は添加効果が小さく、また0.2容積%を越
える場合は腐食を抑制する効果は有るものの正極の二酸
化マンガンの電位劣化が大きくなるので好ましくない。
The addition range of the cationic surfactant is preferably 0.002 to 0.2% by volume with respect to the electrolytic solution. If the amount is less than 0.002% by volume, the effect of addition is small. However, it is not preferable because the potential deterioration of manganese dioxide of the positive electrode increases.

また、該カチオン界面活性剤の添加によって、水銀無
添加の亜鉛または亜鉛合金において腐食が充分抑制され
るが、水銀を少量加えた汞化亜鉛または汞化亜鉛合金に
おいても同等の効果がある。
Further, the addition of the cationic surfactant sufficiently suppresses corrosion in zinc or zinc alloy containing no mercury. However, the same effect can be obtained in zinc-containing mercury or zinc-containing alloy containing a small amount of mercury.

(作 用) 本発明の前記カチオン界面活性剤の添加効果について
は、亜鉛表面に吸着したカチオン界面活性剤のアルキル
が、水素ガス発生反応を阻害することによって腐食を抑
制していると考えられる。
(Operation) Regarding the effect of adding the cationic surfactant of the present invention, it is considered that the alkyl of the cationic surfactant adsorbed on the zinc surface inhibits the hydrogen gas generation reaction, thereby suppressing corrosion.

(実施例) 以下、本発明を実施例、比較例及び参考例にもとづ
き、詳細に説明する。
(Examples) Hereinafter, the present invention will be described in detail based on examples, comparative examples, and reference examples.

実施例1〜10、比較例1〜4及び参考例1 R20亜鉛缶を用いて、縦5.0cm×横9.6cm×厚さ0.04cm
の試験片を作り、そのままのもの(水銀無添加)と、Hg
Cl2溶液を用いて水銀0.005mg/cm2−亜鉛になるように、
表面をアマルガム化したものと2種類を試験に供した。
腐食試験は電解液として、ZnCl2:NH4Cl:H2Oの質量比
が、26:3:71のものを用いて、試験片1枚に対して電解
液60ccの割合で実施した。
Examples 1 to 10, Comparative Examples 1 to 4 and Reference Example 1 Using a R20 zinc can, length 5.0 cm x width 9.6 cm x thickness 0.04 cm
And test specimens (with no mercury added) and Hg
So that the zinc, - Cl 2 solution mercury 0.005 mg / cm 2 using a
Amalgamated surfaces and two types were subjected to the test.
The corrosion test was carried out using an electrolyte having a mass ratio of ZnCl 2 : NH 4 Cl: H 2 O of 26: 3: 71 at a ratio of 60 cc of the electrolyte to one test piece.

そして、炭素数12のアルキル基が、含有アルキル基の
90基数%以上であるカチオン界面活性剤モノアルキル第
四級アンモニウムクロライドの添加量を、電解液に対し
て0〜0.2容積%の範囲の中で種々に変量し、電解液中
への添加試験を行った(実施例1〜10及び比較例1〜
4)。
And the alkyl group having 12 carbon atoms is
The addition amount of the cationic surfactant monoalkyl quaternary ammonium chloride of 90% or more is varied in the range of 0 to 0.2% by volume with respect to the electrolytic solution, and the addition test into the electrolytic solution is performed. (Examples 1 to 10 and Comparative Examples 1 to
4).

また参考として、水銀0.2mg/cm2−亜鉛になるように
アマルガム化した試験片を用い、かつカチオン界面活性
剤無添加のものも同様に試験に供した。(参考例1) 腐食試験の評価は、45℃に15日間保存した後の腐食減
量を測定し、3枚の平均値の腐食減量を単位面積当り
(mg/cm2−亜鉛)で示した。各々の水銀添加量、カチオ
ン界面活性剤添加率及び腐食減量を表1に示す。
For reference, a test piece amalgamated to give 0.2 mg / cm 2 -mercury-zinc and without a cationic surfactant was also used for the test. (Reference Example 1) In the evaluation of the corrosion test, weight loss after storage at 45 ° C. for 15 days was measured, and the average weight loss of the three pieces was shown in terms of unit area (mg / cm 2 -zinc). Table 1 shows the mercury addition amount, the cationic surfactant addition ratio, and the corrosion weight loss.

実施例11〜20、比較例5〜8及び参考例2 電解液として、ZnCl2:NH4Cl:H2Oの質量比が、10:22:6
8のものを用いた以外は実施例1と同様な腐食試験を行
い、それらの結果を表2に示した。
Examples 11 to 20, Comparative Examples 5 to 8 and Reference Example 2 As electrolytes, the mass ratio of ZnCl 2 : NH 4 Cl: H 2 O was 10: 22: 6.
A corrosion test similar to that of Example 1 was performed except that eight samples were used, and the results are shown in Table 2.

実施例21〜30、比較例9〜12及び参考例3 電解液として実施例1と同一組成のものについて、負
極の亜鉛として水銀無添加のものと、水銀0.005mg/cm2
−亜鉛になるように電解液にHgCl2を添加したものとを
使用し、該カチオン界面活性剤添加量を電解液に対し
て、0〜0.5容積%の範囲内で種々に変量し、R20形マン
ガン乾電池を各々10個ずつ試作した。この試作電池を45
℃に3ケ月間保存し、二酸化マンガンの電位劣化を開路
電圧で、亜鉛に対する防食効果を4Ω連続放電の0.9Vま
での持続時間で評価した(実施例21〜30、比較例9〜1
4)。
Example 21-30, for those having the same composition as in Example 1 as Comparative Examples 9 to 12 and Reference Example 3 electrolytic solution as mercury not added as a zinc negative electrode, mercury 0.005 mg / cm 2
- using a material obtained by adding HgCl 2 in the electrolyte solution so that the zinc, the cationic surfactant additive amount of the electrolyte solution, variously and variable in the range of 0 to 0.5 volume%, R20 form Ten prototype manganese batteries were manufactured. 45 of this prototype battery
C. for 3 months, the potential degradation of manganese dioxide was evaluated by the open circuit voltage, and the anticorrosive effect on zinc was evaluated by the duration of 4Ω continuous discharge up to 0.9 V (Examples 21 to 30, Comparative Examples 9-1)
Four).

なお参考として、負極が水銀0.2mg/cm2−亜鉛になる
ように、予じめ電解液にHgCl2を添加し、上記と同様に
マンガン乾電池を試作し、開路電圧及び4Ω連続放電持
続時間を同様に評価した(参考例3)。各々の水銀添加
量、カチオン界面活性剤加率、開路電圧(平均値)及び
4Ω連続放電持続時間(平均値)を表3に示す。
As a reference, HgCl 2 was added to the electrolyte in advance so that the negative electrode became 0.2 mg / cm 2 -zinc mercury. Evaluation was made similarly (Reference Example 3). Table 3 shows the mercury addition amount, cationic surfactant addition rate, open circuit voltage (average value), and 4Ω continuous discharge duration (average value).

実施例31,32 電解液として実施例1と同一組成のものを用い、亜鉛
缶内面にカチオン界面活性剤を、電解液に対して0.05容
積%になる量を塗布したもの(実施例31)、セパレータ
ーに同様に0.05容積%になる量を添加したもの(実施例
32)とを用いて、R20形マンガン乾電池を試作した。こ
れらの乾電池を用い、実施例21と同様に開路電圧及び4
Ω連続放電持続時間を評価し、それらの結果を表3に示
した。
Examples 31 and 32 The same composition as in Example 1 was used as the electrolytic solution, and a cationic surfactant was applied to the inner surface of the zinc can in an amount of 0.05% by volume based on the electrolytic solution (Example 31). A separator to which an amount of 0.05% by volume was similarly added (Example
32), a prototype R20 manganese dry battery was manufactured. Using these batteries, the open circuit voltage and
The continuous discharge duration of Ω was evaluated, and the results are shown in Table 3.

実施例33〜42、比較例15〜20及び参考例4 電解液として実施例11と同一組成のものを用い、実施
例21と同様な方法でマンガン乾電池を試作し、開路電圧
及び4Ω連続放電持続時間を評価した(実施例33〜42、
比較例15〜20)。
Examples 33 to 42, Comparative examples 15 to 20 and Reference example 4 Using an electrolyte having the same composition as in Example 11, a manganese dry battery was prototyped in the same manner as in Example 21, and the open circuit voltage and 4Ω continuous discharge sustained. The time was evaluated (Examples 33-42,
Comparative Examples 15 to 20).

なお、参考例として負極が水銀0.2mg/cm2−亜鉛にな
るように、予じめ電解液にHgCl2を添加し、上記と同様
にマンガン乾電池を試作し、開路電圧及び4Ω連続放電
持続時間を評価した(参考例4)。
As a reference example, HgCl 2 was added to the electrolyte in advance so that the negative electrode became mercury 0.2 mg / cm 2 -zinc, a manganese dry battery was prototyped in the same manner as above, and the open circuit voltage and 4Ω continuous discharge duration Was evaluated (Reference Example 4).

各々の水銀添加量、カチオン界面活性剤添加率、開路
電圧及び4Ω連続放電持続時間を表4に示す。
Table 4 shows the mercury addition amount, cationic surfactant addition ratio, open circuit voltage and 4Ω continuous discharge duration.

実施例43,44 電解液として実施例11と同一組成のものを用い、亜鉛
缶内面に該カチオン界面活性剤を電解液に対して0.05容
積%になる量を塗布したもの(実施例43)、セパレータ
ーに同様に0.05容積%になる量を添加したもの(実施例
44)を用いて、実施例31、32と同様な方法でマンガン乾
電池を試作した。
Examples 43 and 44 The same composition as in Example 11 was used as the electrolytic solution, and the cationic surfactant was applied to the inner surface of the zinc can in an amount of 0.05% by volume based on the electrolytic solution (Example 43). A separator to which an amount of 0.05% by volume was similarly added (Example
44), a manganese dry battery was prototyped in the same manner as in Examples 31 and 32.

これらの電池を用い実施例21と同様に開路電圧及び4
Ω連続放電持続時間を評価し、それらの結果を表4に示
す。
Using these batteries, open circuit voltage and 4
The continuous discharge duration of Ω was evaluated, and the results are shown in Table 4.

表1〜4に示されるごとく、該カチオン界面活性剤を
電解液に対して、0.002〜0.2容積%の範囲で添加したも
のは、亜鉛または亜鉛合金の腐食が著しく抑制され、ま
たマンガン乾電池においては、貯蔵後の開路電圧の劣化
が少なく、放電持続時間が延びていることから、マンガ
ン乾電池の正極作用物質である二酸化マンガンを劣化さ
せることなく、負極である亜鉛缶の腐食を著しく抑制し
ていることが判る。また、カチオン界面活性剤を電解液
に添加させるだけでなく、負極亜鉛缶内に塗布及びセパ
レーターに添加することによっても、同様の効果が得ら
れることが判る。
As shown in Tables 1 to 4, when the cationic surfactant was added in the range of 0.002 to 0.2% by volume with respect to the electrolytic solution, the corrosion of zinc or zinc alloy was remarkably suppressed. Since the open-circuit voltage after storage is less deteriorated and the discharge duration is extended, the corrosion of the negative electrode zinc can is significantly suppressed without deteriorating the manganese dioxide which is the positive electrode active substance of the manganese dry battery. You can see that. Further, it can be seen that the same effect can be obtained not only by adding the cationic surfactant to the electrolytic solution, but also by coating it in the negative electrode zinc can and adding it to the separator.

[発明の効果] 以上、説明したごとく、電池内に電解液に対して、特
定量の炭素数12のアルキル基が、含有アルキル基の90基
数%以上であるカチオン界面活性剤モノアルキル第四級
アンモニウムクロライドを存在させる本発明のマンガン
乾電池は、低水銀化あるいは水銀無添加の場合において
も、正極作用物質である二酸化マンガンを劣化させるこ
となく、負極として用いられる亜鉛または亜鉛合金の腐
食を大幅に低減化でき、工業的価値が大である。
[Effects of the Invention] As described above, the cationic surfactant monoalkyl quaternary in which the specific amount of the alkyl group having 12 carbon atoms is 90% or more of the contained alkyl group with respect to the electrolytic solution in the battery. The manganese dry battery of the present invention in the presence of ammonium chloride can significantly reduce the corrosion of zinc or a zinc alloy used as a negative electrode without deteriorating manganese dioxide, which is a positive electrode active substance, even in the case of low mercury or no mercury added. It can be reduced and has great industrial value.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】塩化亜鉛溶液及び/または塩化アンモニウ
ム溶液を主成分とする電解液を用いるマンガン乾電池に
おいて、該電池内に、炭素数12のアルキル基が、含有ア
ルキル基の90基数%以上であるカチオン界面活性剤モノ
アルキル第四級アンモニウムクロライドを、該電解液に
対して、0.002〜0.2容積%存在させたことを特徴とする
マンガン乾電池。
1. A manganese dry battery using an electrolytic solution containing a zinc chloride solution and / or an ammonium chloride solution as a main component, wherein the number of alkyl groups having 12 carbon atoms is 90% or more of the contained alkyl groups in the battery. A manganese dry battery characterized in that a cationic surfactant monoalkyl quaternary ammonium chloride is present in an amount of 0.002 to 0.2% by volume based on the electrolytic solution.
JP30669689A 1989-11-28 1989-11-28 Manganese dry cell Expired - Lifetime JP2739363B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP30669689A JP2739363B2 (en) 1989-11-28 1989-11-28 Manganese dry cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP30669689A JP2739363B2 (en) 1989-11-28 1989-11-28 Manganese dry cell

Publications (2)

Publication Number Publication Date
JPH03167757A JPH03167757A (en) 1991-07-19
JP2739363B2 true JP2739363B2 (en) 1998-04-15

Family

ID=17960208

Family Applications (1)

Application Number Title Priority Date Filing Date
JP30669689A Expired - Lifetime JP2739363B2 (en) 1989-11-28 1989-11-28 Manganese dry cell

Country Status (1)

Country Link
JP (1) JP2739363B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006103A1 (en) * 1986-04-19 1987-10-22 Terumo Kabushiki Kaisha Process for producing iron-rich foods

Also Published As

Publication number Publication date
JPH03167757A (en) 1991-07-19

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