JPS6177263A - Zinc powder for alkaline battery - Google Patents
Zinc powder for alkaline batteryInfo
- Publication number
- JPS6177263A JPS6177263A JP19674584A JP19674584A JPS6177263A JP S6177263 A JPS6177263 A JP S6177263A JP 19674584 A JP19674584 A JP 19674584A JP 19674584 A JP19674584 A JP 19674584A JP S6177263 A JPS6177263 A JP S6177263A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- zinc powder
- hydrogen gas
- powder
- aqueous 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.)
- Pending
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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の分野）
本発明はアルカリ電池用亜鉛粉に関し、詳しくは亜鉛粉
の表面を亜鉛を溶解させる水溶液で表面処理を施し、水
洗後、乾燥づることにより、未処理の亜鉛粉に比較し、
水素ガス発生を著しく抑制したアルカリ電池用亜鉛粉に
関する。DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to zinc powder for alkaline batteries, and more specifically, the surface of zinc powder is treated with an aqueous solution that dissolves zinc, washed with water, and then dried to form an untreated zinc powder. Compared to zinc powder,
This invention relates to zinc powder for alkaline batteries that significantly suppresses hydrogen gas generation.
（発明の背景）
単位重量当りの電気量が大きく、化学的にも比較的安定
で、加工性に冨み、安価であることからアルカリ電池の
陰極活物質として専らアトマイズされた亜鉛粉が賞用さ
れている。(Background of the invention) Atomized zinc powder is exclusively used as a cathode active material for alkaline batteries because it has a large amount of electricity per unit weight, is relatively stable chemically, has good processability, and is inexpensive. has been done.
しかし、アル７）り電解液の中で′は亜鉛の化学的溶解
によって電池内にガスが蓄積して圧力が１臂し、電解液
の漏出や、電ｉｔ（の変形、はなはだ１）いときには電
池の破壊が起こることがある。その対策どして、従来で
は水銀の水素過電圧を利用１ノだ氷化亜鉛粉が負極活物
質として用いられている。However, due to the chemical dissolution of zinc in the electrolyte, gas accumulates inside the battery and the pressure increases, causing leakage of the electrolyte and (deformation of the electric current). Battery destruction may occur. As a countermeasure, conventionally, icy zinc powder has been used as a negative electrode active material, taking advantage of the hydrogen overvoltage of mercury.
このため、今Ｆ１市販されているアルカリ電池の負極活
物質は５〜１０重鍋％程度の多足の水銀を含有しており
、省令的ニーズどじでより低水銀の電池、あるいは無水
銀の電池の開発が強く期待されるようになってきた。For this reason, the negative electrode active material of F1 alkaline batteries currently on the market contains a large amount of mercury, about 5 to 10% of mercury. There are strong expectations for the development of
そこで電池内の水銀含有率を低減させるべく、水銀以外
の亜鉛の水素ガス発生を抑制する元素を添加した各種亜
鉛粉が提案されているが、いずれも水素ガス発生を抑制
するのには充分で１まなく未だに水銀の使用を避け１ｑ
ぬ現状にある。Therefore, in order to reduce the mercury content in batteries, various zinc powders have been proposed that contain elements other than mercury that suppress hydrogen gas generation from zinc, but none of them are sufficient to suppress hydrogen gas generation. 1. Still avoid the use of mercury 1q
In the current situation.
（発明の目的）
本発明は−に記のような状況に鑑み、これら亜鉛粉の水
素ガス光生抑ｉ！ＩＩｌ効宋をさらに大きくし、しかも
無水銀化が図れるアルカリ電池用叶鉛粉を捉供すること
を目的とする。(Objective of the Invention) In view of the situation described in -, the present invention aims to suppress the hydrogen gas photogenesis of these zinc powders. The purpose of this invention is to obtain and supply lead powder for alkaline batteries that can further increase the effectiveness of the product and also be mercury-free.
（発明の経緯）
本発明者らは上記目的を達成するために種々研究したと
ころ、各種亜鉛粉の表面を酸またはアルカリ等の亜鉛を
溶解さ−１る水溶液で表面処理を施し、水洗後、乾燥す
ることにより得られる亜鉛粉が、このような処理を施さ
ない亜鉛粉に比較し、水素ガス発生が著しく抑制される
という知見を得て本発明に至った。(Background of the invention) In order to achieve the above object, the present inventors conducted various studies and found that the surface of various zinc powders was treated with an aqueous solution such as acid or alkali in which zinc was dissolved, and after washing with water, The present invention was based on the finding that hydrogen gas generation is significantly suppressed in zinc powder obtained by drying compared to zinc powder that is not subjected to such treatment.
（発明の構成）
すなわち本発明は、苛↑４アルカリ水溶液を電解液とす
るアルカリ電池の負極用亜鉛粉において、亜鉛を溶解さ
せる水溶液で表面処理を施し、水洗後、乾燥することに
より得られるアルカリ電池用亜鉛粉にある。(Structure of the Invention) That is, the present invention provides an alkali powder obtained by surface-treating zinc powder for negative electrodes of alkaline batteries using an aqueous ↑4 alkaline solution as an electrolyte with an aqueous solution that dissolves zinc, washing with water, and drying. Found in zinc powder for batteries.
本発明において使用される亜鉛粉とは、亜鉛のみの粉末
のみならず、鉛やインジウム等によって合金化した亜鉛
合金粉も包含される。The zinc powder used in the present invention includes not only a powder of zinc alone but also a zinc alloy powder alloyed with lead, indium, or the like.
本発明において、亜鉛を溶解させる水溶液としては、帽
り硝酸、硫酸、酢酸等の酸の水溶液や水酸化カリウム、
水酸化ナトリウム等のアルカリの水溶液が例示される。In the present invention, examples of the aqueous solution in which zinc is dissolved include aqueous solutions of acids such as nitric acid, sulfuric acid, and acetic acid, potassium hydroxide,
An aqueous alkali solution such as sodium hydroxide is exemplified.
本発明においては、亜鉛粉をこれらの水溶液で表面処理
を施した後、水洗後、乾燥するが、乾燥方法とＩノでは
通常の乾燥方法、１なわち、温風、冷風、赤外線、遠赤
外線等の方法が可能であり、また操作時間短縮のため、
アｔ？トン等の易揮発性溶媒を併用しても良い。また、
乾燥温度も亜鉛の融点以下であれば適宜選択される。In the present invention, zinc powder is surface-treated with these aqueous solutions, washed with water, and then dried. The following methods are possible, and in order to shorten the operation time,
At? Easily volatile solvents such as chlorine and the like may also be used together. Also,
The drying temperature is also appropriately selected as long as it is below the melting point of zinc.
本発明が水素ガス発生を抑制するという効果を右Ｊ−る
理由については明白ではイｃいが、以下の理由が考えら
れる。The reason why the present invention is so effective in suppressing hydrogen gas generation is not obvious, but the following reasons can be considered.
通常、１ＩＴｉ鉛粉はア１〜マイズ法で製造されている
が、この方法であれば一般に表面は粗面となり表面に４
ズや微細な凹凸を生じゃ覆い。腐食の観点から、これら
の部分【ま活性点どなり優先的に腐食が起りや覆い。ず
なわら、水素ガス発生が牛じやすいはずであるが、酸ま
たはアルカリ水溶液等で表面処理を施し、水洗後、乾燥
することにより、新たな平に１頂の高い表面状態になる
と共に、乾燥 ｄ −
によって、その表面に均一な薄い酸化皮膜が形成され、
結果として水素ガス発生を抑制するものと考えられる。Normally, 1ITi lead powder is produced by the a1-mize method, but this method generally results in a rough surface and a
Covers any scratches or minute irregularities. From a corrosion point of view, these parts [are active points, where corrosion preferentially occurs or covers. Naturally, hydrogen gas should be easily generated, but by treating the surface with an acid or alkali aqueous solution, washing with water, and drying, a new high surface condition with a single peak will be created, and it will dry out. d − forms a uniform thin oxide film on its surface,
It is thought that as a result, hydrogen gas generation is suppressed.
また、亜鉛粉の表面に水素ガスの発生を助長する鉄等の
不純物が微量汚染物として混在することが多いが、表面
処理および水洗をすることにより、この不純物が少しで
も除去され、結果的に水素ガス発生を抑制していること
も考えられる。In addition, impurities such as iron that promote the generation of hydrogen gas are often present on the surface of zinc powder as trace contaminants, but by surface treatment and washing with water, even a small amount of these impurities can be removed, resulting in It is also possible that hydrogen gas generation is suppressed.
（発明の実施例）
以下、本発明を亜鉛粉調製例、実施例および比較例に基
づき具体的に説明するが、表面処理液、供用亜鉛粉等は
これに限定されるものではない。(Examples of the Invention) Hereinafter, the present invention will be specifically explained based on zinc powder preparation examples, examples, and comparative examples, but the surface treatment liquid, the zinc powder in use, etc. are not limited thereto.
ｉ糺１１１九
純度９９．９９７％以−トの亜鉛地金を約５００℃で溶
融して、第１表に示す組成並びに含有率になるように元
素（Ｐｂ 、Ｉｎ 、ＴＪ）を添加して亜鉛合金を作成
しこれを高圧空気ガス（噴出圧５Ｋｇ ／ ｃｒｊ ）
を用いて粉体化させた。次いで５０〜１５０メツシユに
なるように篩別し、亜鉛粉（ａ）および亜鉛粉（ｂ）を
調製した。A zinc ingot with a purity of 99.997% or higher is melted at about 500°C, and elements (Pb, In, TJ) are added to the composition and content shown in Table 1. Create a zinc alloy and use it with high pressure air gas (ejection pressure 5Kg/crj)
It was powdered using Next, the powder was sieved to a size of 50 to 150 meshes to prepare zinc powder (a) and zinc powder (b).
４ 一
実施例１〜２
１：１０の１−Ｉ ＣＩ溶液１、！中に亜鉛粉（ａ）お
よび亜鉛粉（ｂ）をそれぞれ１Ｋｇ投入し、常温にて１
０分間撹拌した。次いて・水洗を５回繰返し、濾過後、
１００℃にて渇ＩＪｌ乾燥を行ない、それぞれ本発明の
亜鉛粉（実施例１〜２）を得た。4 Examples 1-2 1:10 1-I CI solution 1,! Pour 1 kg of zinc powder (a) and zinc powder (b) into the container, and heat at room temperature.
Stirred for 0 minutes. Next, repeat washing with water 5 times, and after filtration,
The zinc powder of the present invention (Examples 1 and 2) was obtained by drying at 100°C.
このようにして得られた亜鉛粉を用いて水素ガス′Ｒ，
生試験を行なった。その試験方法は電解液として温度４
０重量％の水酸化カリウム水溶液に酸化亜鉛を飽和さり
たもの５ｍ９ｚ亜鉛粉１０ｇを用いて４５℃で３０日間
のガス発生量を測定した。この結果を第１表に示ず。Using the zinc powder thus obtained, hydrogen gas 'R,
A live test was conducted. The test method is to use the electrolyte at a temperature of 4
Using 10 g of 5m9z zinc powder prepared by saturated zinc oxide in a 0% by weight potassium hydroxide aqueous solution, the amount of gas generated was measured at 45° C. for 30 days. The results are not shown in Table 1.
１通１３〜４
１０重搦％の水酸化カリウム溶液１ノ中に亜鉛粉（ａ）
おにび亜鉛粉（ｂ）をそれぞれ１Ｋｙを投入し、常温に
て３０分間撹拌を行く１つだ。次いで水洗を５回繰返し
、濾過後、４５℃にて真空乾燥を行ない、それぞれ本発
明の亜鉛粉（実施例３へ・４）を得た。Zinc powder (a) in 1 volume of 13-4 10% potassium hydroxide solution
In this case, 1 Ky of rice zinc powder (b) was added and stirred at room temperature for 30 minutes. Next, washing with water was repeated five times, and after filtration, vacuum drying was performed at 45° C. to obtain zinc powders of the present invention (Examples 3 to 4).
このＪ：うにして得られた仙１１）粉を用いて、実施例
１と同様な方法により水素ガス発生試験を行イｆっだ。A hydrogen gas generation test was conducted in the same manner as in Example 1 using this powder obtained by sea urchin.
この結果を第１表に示す。The results are shown in Table 1.
監」乱にＬ
亜鉛粉（ａ＞および亜鉛粉（ワ）を何らの処理を施さず
に、実施例１ど同様の方法により水素ガス発生試験を行
４につだ。イの結果を第１表に示づ。A hydrogen gas generation test was carried out in row 4 using the same method as in Example 1, without any treatment of zinc powder (a) and zinc powder (wa) under supervision. Shown in the table.
第１表に示されること（、亜鉛粉（ａ）おにび亜鉛粉（
ｂ）を、酸（塩酸溶液）またはアルカリ（水酸化カリウ
ム溶液）で表面処理を行ない、次いで水洗し、乾燥を行
なった実施例１〜４の亜鉛粉は、亜鉛粉（ａ）および亜
鉛粉（ｂ）に何ら処理を施さなかった比較例１〜２に比
較１ノで水素ガス発生が著しく抑制されている。What is shown in Table 1 (zinc powder (a) rice zinc powder (
Zinc powder (a) and zinc powder ( Hydrogen gas generation was significantly suppressed in Comparative Examples 1 and 2, in which no treatment was applied to b), and in Comparative Example 1.
（発明の効果）
以上説明のごとく、亜鉛粉の表面を亜鉛を溶解させる水
溶液で表面処理を施し、水洗後、乾燥することにより４
ｑられる本発明のアルカリ電池用亜鉛粉は、水素ガスの
発生を著しく抑制することから、アルカリ電池の負極ど
して好適に用いられ、その工業的価値は大である。(Effects of the invention) As explained above, the surface of zinc powder is treated with an aqueous solution that dissolves zinc, washed with water, and then dried.
The zinc powder for alkaline batteries of the present invention is suitably used as a negative electrode of alkaline batteries because it significantly suppresses the generation of hydrogen gas, and has great industrial value.
特許出願人 三井金属鉱業株式会社 代理人 弁理士 伊 東 辰 雄 代理人 弁理士 伊 東 哲 也 一りｎクーPatent applicant: Mitsui Metal Mining Co., Ltd. Agent: Patent Attorney Tatsuo Ito Agent: Patent Attorney Tetsuya Ito One n coo
Claims (1)
負極用亜鉛粉において、亜鉛を溶解させる水溶液で表面
処理を施し、水洗後、乾燥することにより得られるアル
カリ電池用亜鉛粉。1. Zinc powder for negative electrodes of alkaline batteries using an aqueous caustic alkali solution as the electrolyte, surface-treated with an aqueous solution that dissolves zinc, washed with water, and then dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19674584A JPS6177263A (en) | 1984-09-21 | 1984-09-21 | Zinc powder for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19674584A JPS6177263A (en) | 1984-09-21 | 1984-09-21 | Zinc powder for alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6177263A true JPS6177263A (en) | 1986-04-19 |
Family
ID=16362896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19674584A Pending JPS6177263A (en) | 1984-09-21 | 1984-09-21 | Zinc powder for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6177263A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437224A (en) * | 1977-08-29 | 1979-03-19 | Shin Kobe Electric Machinery | Alkaline cell |
-
1984
- 1984-09-21 JP JP19674584A patent/JPS6177263A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437224A (en) * | 1977-08-29 | 1979-03-19 | Shin Kobe Electric Machinery | Alkaline cell |
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