JPS61116755A - Zinc powder for alkaline manganese battery and alkaline manganese battery - Google Patents
Zinc powder for alkaline manganese battery and alkaline manganese batteryInfo
- Publication number
- JPS61116755A JPS61116755A JP59237953A JP23795384A JPS61116755A JP S61116755 A JPS61116755 A JP S61116755A JP 59237953 A JP59237953 A JP 59237953A JP 23795384 A JP23795384 A JP 23795384A JP S61116755 A JPS61116755 A JP S61116755A
- Authority
- JP
- Japan
- Prior art keywords
- zinc powder
- less
- battery
- alkaline manganese
- zinc
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、Ｈｇを含まなくてもアルカリマンガン電池
の活物質として用いた場合に、Ｈｇとアマルガム化され
た亜鉛からなる従来の活物質とほぼ同等の自己放電防止
作用及び不動体化現象の回避作用を有する、特定の不純
物の含有量合計が特定の値より少ないアルカリマンガン
電池用亜鉛粉末と、前記亜鉛粉末を、Ｋｇを加えること
なく陰極活物質とした、保存寿命及び連続放電時間の長
いアルカリマンガン電池に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method that can be used as an active material of an alkaline manganese battery even if it does not contain Hg, compared to a conventional active material consisting of Hg and amalgamated zinc. Zinc powder for alkaline manganese batteries, which has almost the same self-discharge prevention effect and passivation avoidance effect, and whose total content of specific impurities is less than a specific value, and the zinc powder are used as a cathode without adding Kg. This invention relates to an alkaline manganese battery having a long shelf life and continuous discharge time, using the active material as an active material.
電気製品の普及とそのコードレス化に伴なって、電池の
需要が著増しているが、中でも安価で性能の秀れたアル
カリマンガン電池（いわゆる乾電池〕が多量に消費され
ている。現在使用されているアルカリマンガン電池は基
本構造として苛性アルカリを電解質、二酸化マンガン（
多くは電解二酸化マンガン〕を陽極活物質、ＨｇをｌＯ
％程度加えてアマルガム化した亜鉛粉末を陰極活物質と
している。With the spread of electrical appliances and their becoming cordless, the demand for batteries has increased significantly, and among them, alkaline manganese batteries (so-called dry batteries), which are inexpensive and have excellent performance, are being consumed in large quantities. The basic structure of alkaline manganese batteries is caustic alkali as an electrolyte and manganese dioxide (
In many cases, electrolytic manganese dioxide] is used as the anode active material, and Hg is used as the anode active material.
The cathode active material is zinc powder that has been amalgamated with about 10% of the total amount of zinc powder.
電気亜鉛あるいは蒸溜（常圧蒸溜］亜鉛のような工業的
に得られる亜鉛を原料とし、噴霧法により製造した亜鉛
粉末（原料が電気亜鉛の場合の亜鉛粉末の不純物含量は
鉄：５〜２０ｐｐｍ、カドミウム：１〜５ｐｐｍ、銅：
１〜１０ｐｐｍ、ニッケル：１〜５ｐｐｍ、 コバル
ト：０．１〜ｉ ｐｐｍ 、銀：１〜５ｐｐｍ等；原料
が蒸溜（常圧蒸溜）亜鉛の場合の亜鉛粉末の不純物含量
は鉄：１００〜３００ｐｐｍ 、カドミウム： ５０〜
１０００ｐｐｍ、銅：１０〜１００ｐｐｍ、 ニッケル
：１〜３０ｐｐｍ、コバルト：１〜１０ｐｐｍ、銀：
１〜１０ｐｐｍ等ンを単独で陰極活物質として用いた場
合には、電池が無負荷の状態でも、該亜鉛粉末が電解質
中で水素を放出して電解質溶液中に溶は込んで行く、い
わゆる自己放電現象を惹起し、電池の寿命を著しくアマ
ルガム化し、陰極活物質として使用しているのである。Zinc powder produced by a spraying method using industrially obtained zinc such as electrolytic zinc or distilled (normal pressure distilled) zinc as a raw material (when the raw material is electrolytic zinc, the impurity content of the zinc powder is iron: 5 to 20 ppm, Cadmium: 1-5ppm, copper:
1 to 10 ppm, nickel: 1 to 5 ppm, cobalt: 0.1 to i ppm, silver: 1 to 5 ppm, etc.; when the raw material is distilled (atmospheric pressure distilled) zinc, the impurity content of zinc powder is iron: 100 to 300 ppm, Cadmium: 50~
1000ppm, copper: 10-100ppm, nickel: 1-30ppm, cobalt: 1-10ppm, silver:
When 1 to 10 ppm of zinc powder is used alone as a cathode active material, the zinc powder releases hydrogen in the electrolyte and dissolves into the electrolyte solution even when the battery is under no load. It causes a discharge phenomenon, significantly shortening the life of the battery, and is used as a cathode active material.
こうすることにより、電池の無負荷状態での亜鉛粉末の
電解質溶液中への自然溶解現象（自己放電］が著しく低
減し、かつ電池の負荷時に次第に亜鉛粉末の溶解が妨げ
られるようになる、いわゆる不動体化現象を回避するこ
とができるのである。By doing this, the phenomenon of spontaneous dissolution of zinc powder into the electrolyte solution (self-discharge) when the battery is under no load is significantly reduced, and the so-called dissolution of zinc powder is gradually prevented when the battery is loaded. This makes it possible to avoid the phenomenon of immobilization.
しかるに、Ｈｇは言うまでもなく人体に有害な物質であ
り、アルカリマンガン電池の製造工程での作業者の保護
対策に多大の費用が必要であり、かつまた近年の電気製
品のコードレス化に伴９！池使用量の著増の結果、使用
済電池の廃棄所からの水銀の漏洩による環境汚染が新た
な社会問題となり、従って狗を含まずとも、電池性能の
優れたアルカリマンガン電池の、要求が社会的に急速に
高まっている。However, it goes without saying that Hg is a substance that is harmful to the human body, and a large amount of money is required to protect workers in the manufacturing process of alkaline manganese batteries.Moreover, as electrical products have become cordless in recent years, Hg has become more expensive. As a result of the significant increase in the amount of ponds used, environmental pollution due to leakage of mercury from used battery disposal sites has become a new social problem.Therefore, there is a growing social demand for alkaline manganese batteries with excellent battery performance, even if they do not contain dogs. is rapidly increasing.
我々は今まで、亜鉛の高純度化（例えば、電気亜鉛の蒸
溜による高純度化）とその耐食性等の特性について種々
研究を進めてきたが、亜鉛の純度用活物質への応用を試
みた結果、在来の亜鉛中に検出される不純物であるＦｅ
、 Ｃｕ、 Ｐｂ、 Ｃｄ、 Ｓｂ。Until now, we have been conducting various research on the high purity of zinc (for example, high purity through electrolytic zinc distillation) and its properties such as corrosion resistance. , Fe, an impurity detected in conventional zinc
, Cu, Pb, Cd, Sb.
Ｓｎ、 Ｍｎ、 Ｎｉ、 Ｃｏ、 Ａｇ等のうち鉄、力
）”ラム。Among Sn, Mn, Ni, Co, Ag, etc., iron, force)” Ram.
銅、ニッケル、コバルト、及び銀の含有量合計をある特
定量よりも低減した亜鉛粉末を使用丁れば、Ｈｇによる
アマルガム化の助けを借りなくとも、アルカリマンガン
電池電解質中での自己放電が著しく少なく、前述の不動
体化現象もみられず、陰極活物質としてＨｇを加えた従
来品に匹敵する電池性能が得らｎることを見い出した。Using zinc powder with a total copper, nickel, cobalt, and silver content lower than a certain amount will significantly reduce self-discharge in alkaline manganese battery electrolytes without the aid of Hg amalgamation. It was found that the above-mentioned passivation phenomenon was not observed, and battery performance comparable to conventional products in which Hg was added as a cathode active material could be obtained.
この発明は、上記知見に基いて発明されたものであり、 （１） 鉄、カドミウム、銅、ニッケル、コバルト。This invention was invented based on the above knowledge, (1) Iron, cadmium, copper, nickel, cobalt.
及び銀の含有量合計が９ ｐｐｍ以下であることを特徴
とするアルカリマンガン電池用亜鉛粉末。and a zinc powder for an alkaline manganese battery, characterized in that the total content of silver is 9 ppm or less.
■ 鉄、カドミウム、銅、ニッケル、コバルト。■ Iron, cadmium, copper, nickel, cobalt.
及び銀の含有量合計が９ｐｐｍ以下である亜鉛粉末を、
水銀を加えることなく陰極活物質としたアルカリマンガ
ン電池である。and zinc powder with a total silver content of 9 ppm or less,
This is an alkaline manganese battery that uses the cathode active material without adding mercury.
以下、この発明の詳細な説明する。The present invention will be explained in detail below.
亜鉛粉末中の不純物である鉄、カドミウム、銅。Iron, cadmium, and copper are impurities in zinc powder.
ニッケル、コバルト、及び鋼の含有量合計が９ｐｐｍを
越えると、この亜鉛粉末を単独でアルカリマンガン電池
の陰極活物質として用いたとき、自己放電現象が発生し
て、無負荷でも活物質である亜鉛末が溶解することとな
り、しかも、不動体化現象が顕在化して、ひいては、こ
の亜鉛粉末を、Ｈｇを加えることなく陰極活物質とした
アルカリマンガン電池の保存寿命が１年未満となシ、か
つ連続放電時間が５時間未満となるから、亜鉛粉末中の
不純物である鉄、カドミウム、銅、ニッケル、コバルト
、及び銀の含有量合計を９ ｐｐｍ以下と定めた。好
ましくは、前記の不純物の含有量合計は５ｐｐｍ未満で
ある。If the total content of nickel, cobalt, and steel exceeds 9 ppm, when this zinc powder is used alone as a cathode active material in an alkaline manganese battery, a self-discharge phenomenon will occur, and the active material zinc will dissipate even under no load. Moreover, the passivation phenomenon becomes obvious, and as a result, the shelf life of an alkaline manganese battery using this zinc powder as a cathode active material without adding Hg becomes less than one year. Since the continuous discharge time was less than 5 hours, the total content of impurities iron, cadmium, copper, nickel, cobalt, and silver in the zinc powder was determined to be 9 ppm or less. Preferably, the total content of said impurities is less than 5 ppm.
なお、この鉄、カドミウム、銅、ニッケル、コバルト、
及び銀の含有量合計が９ｐｐｍ以下である亜鉛粉末とし
ては、蒸溜（常圧蒸溜）亜鉛よりも高純度な電気亜鉛を
原料とし、常圧又は真空で蒸溜することにより精製し、
このようにして得られた精製亜鉛を噴霧して得らｎたも
の、電気亜鉛を消耗陽極とした再電解精製亜鉛を噴霧し
たもの等を用いることができる。In addition, this iron, cadmium, copper, nickel, cobalt,
Zinc powder with a total silver content of 9 ppm or less is made from electrolytic zinc, which is purer than distilled (normal pressure distilled) zinc, and purified by distillation at normal pressure or vacuum.
Those obtained by spraying the purified zinc thus obtained, those obtained by spraying re-electrolyzed refined zinc using electrolytic zinc as a consumable anode, etc. can be used.
〔実施例〕
以下、実施例により、この発明の構成及び効果を説明す
る。[Example] Hereinafter, the structure and effects of the present invention will be explained with reference to Examples.
実施例１
電気亜鉛を噴霧して得た従来亜鉛粉末（Ａ）、及び該電
気亜鉛を真空蒸溜（真空度： ６０ｔｏｒｒ 。Example 1 Conventional zinc powder (A) obtained by spraying electrolytic zinc, and vacuum distillation of the electrolytic zinc (degree of vacuum: 60 torr).
温度：８９０℃、蒸溜塔の棚段数：２段、還流率ニア０
％）により精製後、噴霧して得几本発明亜鉛粉末（Ｂ）
を用意した。Temperature: 890°C, number of plates in distillation column: 2, reflux rate near 0
%) and then sprayed to obtain zinc powder (B) of the present invention.
prepared.
従来亜鉛粉末Ａ並びに本発明亜鉛粉末Ｂの鉄。Iron of conventional zinc powder A and zinc powder B of the present invention.
カドミウム、銅、ニッケル、コノくルト、及び銀の含有
量合計は、それぞれ３６ｐｐｍ及び１．４ｐｐｍであっ
た。The total content of cadmium, copper, nickel, conorct, and silver was 36 ppm and 1.4 ppm, respectively.
従来亜鉛粉末Ａ及び本発明亜鉛粉末Ｂのそれぞ） を、
アルカリマンガン電池の電解質と同濃度（’ ３ｏｘ
＞。６カ１．。ｃＨｃｆｉ［ｔ、、 ｎａｉｇａａを測
定し友。Conventional zinc powder A and present invention zinc powder B),
The same concentration as the electrolyte in alkaline manganese batteries ('3ox
>. 6 Ka1. . Measuring cHcfi [t,, naigaa.
その結果、従来亜鉛粉末Ａ１本発明亜鉛粉末Ｂ。As a result, the conventional zinc powder A1 and the present invention zinc powder B.
従来亜鉛粉末Ａのアマルガム及び本発明亜鉛粉末Ｂのア
マルガムの自己溶解性は、−それぞれ７．３ｍＪｉｌ
／ ｄｉ’−ｈｒ、 、 ０．０６ ｍＪｉ／ ｄ１ｒ
Ｌ″・ｈｒ、、 ０．０５ｍｖｄｍ’・ｈｒ。The self-dissolution properties of the amalgam of conventional zinc powder A and the amalgam of zinc powder B of the present invention are -7.3 mJil, respectively.
/di'-hr, , 0.06 mJi/d1r
L″・hr,, 0.05mvdm′・hr.
及び０．０１ ｍＪｉ／ ｄｍ”・ｈｒ、未満であり、
本発明亜鉛粉末Ｂ、従来亜鉛粉末Ａのアマルガム及び本
発明亜鉛粉末Ｂのアマルガムの自己溶解性は、従来亜鉛
粉末人のそれの１００分の１未満であった。and less than 0.01 mJi/dm”・hr,
The self-dissolution of the amalgam of the zinc powder B of the present invention, the amalgam of the conventional zinc powder A, and the amalgam of the zinc powder B of the present invention was less than 1/100 of that of the conventional zinc powder.
そこで、自己溶解性の認められなかつ之本発明亜鉛粉末
Ｂ、従来亜鉛粉末人のアマルガム及び本発明亜鉛粉末Ｂ
のアマルガムをそれぞれ陰極活物質として単３規格のア
ルカリマンガン電池を形成して、無負荷時の保存寿命と
１０オーム負荷使用のときの連続放電時間を測定した。Therefore, the zinc powder B of the present invention which is not recognized to be self-dissolving, the amalgam of the conventional zinc powder, and the zinc powder B of the present invention.
AA-sized alkaline manganese batteries were formed using the amalgams as cathode active materials, and the storage life under no load and the continuous discharge time when using a 10 ohm load were measured.
その結果、保存寿命は、王者共に２年以上であり、又、
連続放電時間は、本発明亜鉛粉末Ｂでは７９０分、従来
亜鉛粉末Ａのアマルガムでは８３０分、そして、本発明
亜鉛粉末Ｂのアマルガムでは８４０分であった。As a result, the shelf life of both champions is over 2 years, and
The continuous discharge time was 790 minutes for the zinc powder B of the present invention, 830 minutes for the amalgam of the conventional zinc powder A, and 840 minutes for the amalgam of the zinc powder B of the present invention.
実施例２
実施例１の従来亜鉛粉末Ａの原料亜鉛と本発明亜鉛粉末
Ｂの原料亜鉛とを混合溶融径噴霧して、鉄、カドミウム
、銅、ニッケル、コバルト、及び銀の含有量合計が下記
の表のように種々の亜鉛粉末を得几。Example 2 The raw material zinc for the conventional zinc powder A in Example 1 and the raw material zinc for the present invention zinc powder B were mixed and sprayed in a molten size, and the total content of iron, cadmium, copper, nickel, cobalt, and silver was as follows. Various zinc powders are obtained as shown in the table below.
これらの亜鉛粉末を用いて、それぞｎ単３規格のアルカ
リマンガン電池を同じ亜鉛粉未使用のものにつき１０個
ずつ製作し、それぞれの電池の無負荷時の保存寿命と１
０オーム負荷使用のときの連続放電時間を測定した。種
々の不純物含有量を有する亜鉛粉末を用いたときの、１
０個の電池の保存寿命の平均値と１０個の電池の連続放
電時間の平均値をそれぞれ下記の表に示す。Using these zinc powders, we manufactured 10 AA-sized alkaline manganese batteries each without using zinc powder, and measured the no-load storage life and 1 of each battery.
Continuous discharge time was measured when using a 0 ohm load. 1 when using zinc powder with various impurity contents
The average value of the shelf life of 0 batteries and the average value of continuous discharge time of 10 batteries are shown in the table below, respectively.
実施例１．２の結果から、従来のアルカリマンガン電池
用亜鉛粉末の場合は単独では、即ちＨｇを添加しないと
自己溶解性から電池の陰極活物質として全く実用化する
ことができないのに対して、この発明の亜鉛粉末中の該
不純物含有量を９ｐｐｍ以下に低減したものを用いれば
、問題の多いＨｇを添加しなくても、従来の水銀アマル
ガムを含む電池とほぼ同様の実用性能を持った電池の得
られることがわかる。From the results of Example 1.2, in the case of conventional zinc powder for alkaline manganese batteries, it cannot be put to practical use as a cathode active material for batteries at all due to self-dissolution unless Hg is added. By using the zinc powder of the present invention in which the content of impurities is reduced to 9 ppm or less, it is possible to achieve practically the same practical performance as a conventional battery containing mercury amalgam without adding problematic Hg. It can be seen that the battery can be obtained.
Claims (2)
銀の含有量合計が９ｐｐｍ以下であることを特徴とする
アルカリマンガン電池用亜鉛粉末。(1) Zinc powder for alkaline manganese batteries, characterized in that the total content of iron, cadmium, copper, nickel, cobalt, and silver is 9 ppm or less.
銀の含有量合計が９ｐｐｍ以下である亜鉛粉末を、水銀
を加えることなく陰極活物質としたアルカリマンガン電
池。(2) An alkaline manganese battery in which zinc powder with a total content of iron, cadmium, copper, nickel, cobalt, and silver of 9 ppm or less is used as a cathode active material without adding mercury.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59237953A JPS61116755A (en) | 1984-11-12 | 1984-11-12 | Zinc powder for alkaline manganese battery and alkaline manganese battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59237953A JPS61116755A (en) | 1984-11-12 | 1984-11-12 | Zinc powder for alkaline manganese battery and alkaline manganese battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61116755A true JPS61116755A (en) | 1986-06-04 |
| JPH0355024B2 JPH0355024B2 (en) | 1991-08-22 |
Family
ID=17022910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59237953A Granted JPS61116755A (en) | 1984-11-12 | 1984-11-12 | Zinc powder for alkaline manganese battery and alkaline manganese battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61116755A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0500313A2 (en) * | 1991-02-19 | 1992-08-26 | Mitsui Mining & Smelting Co., Ltd. | Zinc alloy powder for alkaline cell and method to produce the same |
| JPH0586430A (en) * | 1991-02-19 | 1993-04-06 | Mitsui Mining & Smelting Co Ltd | Zinc alloy powder for alkali battery and its production |
| JPH05166507A (en) * | 1991-10-16 | 1993-07-02 | Mitsui Mining & Smelting Co Ltd | Zinc alloy powder for alkaline battery and its manufacture |
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
| US5626988A (en) * | 1994-05-06 | 1997-05-06 | Battery Technologies Inc. | Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture |
| EP0845827A2 (en) * | 1990-08-14 | 1998-06-03 | Eveready Battery Company, Inc. | Substantially mercury-free electrochemical cells |
-
1984
- 1984-11-12 JP JP59237953A patent/JPS61116755A/en active Granted
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0845827A2 (en) * | 1990-08-14 | 1998-06-03 | Eveready Battery Company, Inc. | Substantially mercury-free electrochemical cells |
| EP0845827A3 (en) * | 1990-08-14 | 2002-06-19 | Eveready Battery Company, Inc. | Substantially mercury-free electrochemical cells |
| EP0500313A2 (en) * | 1991-02-19 | 1992-08-26 | Mitsui Mining & Smelting Co., Ltd. | Zinc alloy powder for alkaline cell and method to produce the same |
| JPH0586430A (en) * | 1991-02-19 | 1993-04-06 | Mitsui Mining & Smelting Co Ltd | Zinc alloy powder for alkali battery and its production |
| JPH0754704B2 (en) * | 1991-02-19 | 1995-06-07 | 三井金属鉱業株式会社 | Zinc alloy powder for alkaline battery and method for producing the same |
| JPH05166507A (en) * | 1991-10-16 | 1993-07-02 | Mitsui Mining & Smelting Co Ltd | Zinc alloy powder for alkaline battery and its manufacture |
| JPH0754705B2 (en) * | 1991-10-16 | 1995-06-07 | 三井金属鉱業株式会社 | Zinc alloy powder for alkaline battery and method for producing the same |
| JPH076759A (en) * | 1992-08-04 | 1995-01-10 | Seiko Instr Inc | Alkaline battery, manufacture thereof, and appliance using alkaline battery |
| US5626988A (en) * | 1994-05-06 | 1997-05-06 | Battery Technologies Inc. | Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0355024B2 (en) | 1991-08-22 |
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