JPS6032248A - Zinc and zinc alloy for negative electrode of primary battery - Google Patents
Zinc and zinc alloy for negative electrode of primary batteryInfo
- Publication number
- JPS6032248A JPS6032248A JP58139494A JP13949483A JPS6032248A JP S6032248 A JPS6032248 A JP S6032248A JP 58139494 A JP58139494 A JP 58139494A JP 13949483 A JP13949483 A JP 13949483A JP S6032248 A JPS6032248 A JP S6032248A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- silver
- alloy
- gallium
- indium
- 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
- H01M4/36—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、負極用として耐食性および放電利用率にすぐ
れた一次電池負極用銀被着亜鉛および銀−亜鉛基合金に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to silver-coated zinc and silver-zinc-based alloys for primary battery negative electrodes that have excellent corrosion resistance and discharge utilization.
従来−次電池においては、電池貯蔵時における高い耐食
性と使用放電時にｊｒける高い亜鉛（り用率を得るため
に、６〜１０％の水銀を亜鉛粒子表面に被覆ないし合金
化させたものが負極として使用されてきているが、最近
−次電池の需要の伸びから、このような水銀を含む使用
済み一次電池の廃１η処分が公害発生の懸念により問題
視されるようになっており、−次電池用として低氷化な
いし無氷化亜鉛負極の開発が切望されてきている。Conventionally, in secondary batteries, in order to obtain high corrosion resistance during battery storage and high zinc usage rate during use and discharge, the negative electrode is coated or alloyed with 6 to 10% mercury on the surface of zinc particles. However, due to the recent growth in demand for secondary batteries, the disposal of used primary batteries containing mercury has become a problem due to concerns about pollution. There is a strong desire to develop a low-icing or no-icing zinc negative electrode for use in batteries.
しかし、現在−次電池用負極として使用されている氷化
亜鉛は高い耐食性を有するのみならず、亜鉛の放電利用
千は９０％を越え、性能の面からはすぐれた電極材料で
ある。これまで無氷化ないし低木化条件下での代替材と
してガリウム、インジウム、鉛、ビスマス、タリウム等
の金属元素を添加した亜鉛合金、あるいは塩類水溶液中
の処理でそれら金属元素を表面に直換被着させた亜鉛な
どいろいろ試みられており、耐食性については氷化亜鉛
に匹敵する値を有するものが提供されるようになってき
ている。しかしながら、一方の亜鉛利用率の面ではまだ
問題が残されている。従来の単純な無氷化亜鉛の場合で
は、放電使用の際にみられる放電生成物が表面を覆って
固着して流電を妨げ、逐には電気化学的不働態となり、
結果的に亜鉛の放電利用率はたとえば４０％というよう
なかなりの低率に止まることになるものである。これま
で、前記のようなガリウム等を含む高耐食性亜鉛合金あ
るいは合金被着亜鉛によって若干改善はされており、た
とえば特開昭５８−２６４５６号にみられるガリウム−
インジウム−亜鉛合金では放電利用率が８５係程度にま
で向上しているが、まだ充分にンに１足されているとは
いえない。However, frozen zinc, which is currently used as a negative electrode for rechargeable batteries, not only has high corrosion resistance, but also has a discharge utilization rate of over 90%, making it an excellent electrode material in terms of performance. Until now, zinc alloys to which metal elements such as gallium, indium, lead, bismuth, and thallium have been added have been used as substitute materials under conditions of no ice or shrub formation, or those metal elements have been directly converted to the surface by treatment in an aqueous salt solution. Various attempts have been made, such as zinc coating, and products with corrosion resistance comparable to that of frozen zinc are now available. However, problems still remain in terms of zinc utilization. In the case of conventional simple ice-free zinc, discharge products seen during discharge use cover and stick to the surface, impeding current flow, and eventually becoming electrochemically passive.
As a result, the discharge utilization rate of zinc remains at a fairly low rate of, for example, 40%. Up to now, some improvements have been made using highly corrosion-resistant zinc alloys containing gallium, etc., or zinc alloy coatings.
In indium-zinc alloys, the discharge utilization rate has improved to about 85 coefficients, but it cannot be said that it has been sufficiently improved.
本発明は、このような−次電池負極用亜鉛合金に関し、
無氷化ないし低汞化条件下で高い耐食性と高い放電利用
率を示す亜鉛または亜鉛合金の提供を目的としたもので
あり、純亜鉛を銀塩水溶液とガリウム、インジウム、鉛
、ビスマスおよびタリウムのうちの１つまたは２つ以上
の金属元素の塩類水溶液とで処理して表面に銀または銀
を含む前記金属元素の置換層を被着させた一次電池負極
用亜鉛、あるいはガリウム、インジウム、鉛、ビスマス
およびタリウムのうちの１つか２つ以上の金属元素と銀
とを含む亜鉛合金を銀塩水溶液で処理して銀の置換層を
被着させた一次電池負極用亜鉛合金である。The present invention relates to such a zinc alloy for secondary battery negative electrodes,
The purpose is to provide zinc or zinc alloys that exhibit high corrosion resistance and high discharge utilization under ice-free or low-fragrance conditions. Zinc for primary battery negative electrodes, treated with an aqueous salt solution of one or more of the metal elements to deposit a substitution layer of silver or the metal element containing silver on the surface, or gallium, indium, lead, This zinc alloy for primary battery negative electrodes is prepared by treating a zinc alloy containing silver and one or more metal elements of bismuth and thallium with an aqueous silver salt solution to deposit a silver substitution layer.
本発明者等は、銀の酸化物が電気伝導度にすぐれている
こと、および電解液や腐食性水溶液等における銀−亜鉛
合金ではイオン化傾向の差により亜鉛が優先的に溶解し
銀が残留することに着目し、その電池特性の調査検耐を
行なったものである。The present inventors have discovered that silver oxide has excellent electrical conductivity, and that in silver-zinc alloys in electrolytes and corrosive aqueous solutions, zinc preferentially dissolves and silver remains due to differences in ionization tendency. Focusing on this, we conducted an investigation and test of the battery characteristics.
その結果純亜鉛の表面に０．０５％以上の銀を被着させ
た亜鉛、特には銀０．０１％以上と同時に耐食性改善金
属であるところのガリウム、インジウム、鉛、ビスマス
およびタリウムのうち１つまたは２つ以上を０．００５
％以上複合的に混在ないし合金化状態で被着させた亜鉛
は耐食性とともに、放電使用時の亜鉛利用率が著しく高
められていることが見出された。すなわち亜鉛利用率は
９０％を越え耐食性と共に氷化亜鉛と同等以上の効果を
有することが見出された。特に后者においては明らかに
被着Ｍにおける銀と前記ガリウム等金属元素との相乗効
果が見られたのである。これは、電池の放電使用中に生
成するいわゆる放電生成物の被膜中に銀が残留し、これ
が導電経路となり、亜鉛の不働態化を阻み、活性状態を
維持するものと考えられ、さらに前記ガリウム等耐食性
改善金属の効果が相乗的に加算されるものと考えられる
。As a result, zinc with 0.05% or more silver coated on the surface of pure zinc, especially 1 of gallium, indium, lead, bismuth, and thallium, which are metals that improve corrosion resistance at the same time as 0.01% or more silver. 0.005 for one or more
It has been found that when zinc is deposited in a mixed or alloyed state in a mixed or alloyed state in an amount of % or more, not only the corrosion resistance but also the zinc utilization rate during discharge use is significantly increased. In other words, it was found that the zinc utilization rate exceeds 90%, and that it has corrosion resistance and an effect equal to or higher than that of frozen zinc. Particularly in the latter case, a synergistic effect between silver in the deposit M and the metal element such as gallium was clearly observed. This is thought to be because silver remains in the film of so-called discharge products generated during discharge use of the battery, which becomes a conductive path, prevents zinc from becoming passivated, and maintains the active state. It is thought that the effects of corrosion resistance-improving metals are added synergistically.
純亜鉛に対する前記ガリウム等耐食性改善金属の被着の
ための塩類水溶液の処理および銀被着のための銀塩水溶
液の処理は通常別個の処理であって順次行なわれる。塩
類水溶液は塩化物水溶液、硫酸塩水溶液、チオ硫酸塩水
溶液等が用いられ、この中に亜鉛粒子を投入攪拌するこ
とで亜鉛表面への銀等金属の置換被着が行なわれる。The treatment of pure zinc with an aqueous salt solution for depositing the corrosion resistance improving metal such as gallium and the treatment with an aqueous silver salt solution for depositing silver are usually separate treatments and are carried out sequentially. As the aqueous salt solution, a chloride aqueous solution, a sulfate aqueous solution, a thiosulfate aqueous solution, etc. are used, and by introducing zinc particles into the solution and stirring, metals such as silver are deposited on the zinc surface by displacement.
また、これらの知見に加え、純亜鉛に前記ガリウム、イ
ンジウム、鉛、ビスマスおよびタリウムという耐食性改
善金属のうちの１つまたは２つ以上を０．０１％以上予
め添加し合金化せしめておき、これを銀塩水溶液で処理
し銀を合金表面に置換被着させることによって、上記複
合被着の場合と同様無氷化負極材として有効なものであ
ることが見出されている。In addition to these findings, we have added 0.01% or more of one or more of the corrosion resistance improving metals, gallium, indium, lead, bismuth, and thallium, to pure zinc in advance to form an alloy. It has been found that by treating silver with an aqueous silver salt solution to deposit silver on the alloy surface by substitution, it is effective as an ice-free negative electrode material, similar to the case of the composite deposition described above.
なお本発明は、主として無氷化亜鉛または無氷化亜鉛合
金の開発を意図してなされたものであって、その面での
効果も主張されるものであるが、本発明は低氷化処理に
よって銀ないし前記ガリウム等耐食性改善金属の節減を
図ることを妨げるものではない。The present invention was mainly made with the intention of developing ice-free zinc or ice-free zinc alloys, and the present invention is also claimed to be effective in that respect. However, this does not prevent the use of corrosion resistance improving metals such as silver or the above-mentioned gallium to be reduced.
特許出願人 東邦亜鉛株式会社 １“、・１１ソPatent applicant: Toho Zinc Co., Ltd. 1",・11 so
Claims (2)
およびタリウムのうちの１つまたは２つ以上の金属元素
および銀のそれぞれの塩類水溶液で順次処理して表面に
銀を含−む前記金属元素の置換層を被着せしめたことを
特徴とする一次電池負極用亜鉛(1) The metal element containing silver on the surface by sequentially treating pure zinc with an aqueous salt solution of one or more metal elements of gallium 2, indium, lead, bismuth, and thallium and silver. Zinc for primary battery negative electrode characterized by having a replacement layer of
よびタリウムのうちの１つまたは２つ以上の金属元素を
添加した亜鉛合金を銀塩水溶液で処理し、表面に置換層
を被着せしめた一次電池負極用亜鉛基合金。(2) A primary zinc alloy made by adding one or more metal elements of gallium, indium, lead, bismuth, and thallium to pure zinc is treated with a silver salt aqueous solution and a substitution layer is deposited on the surface. Zinc-based alloy for battery negative electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58139494A JPS6032248A (en) | 1983-08-01 | 1983-08-01 | Zinc and zinc alloy for negative electrode of primary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58139494A JPS6032248A (en) | 1983-08-01 | 1983-08-01 | Zinc and zinc alloy for negative electrode of primary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6032248A true JPS6032248A (en) | 1985-02-19 |
Family
ID=15246569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58139494A Pending JPS6032248A (en) | 1983-08-01 | 1983-08-01 | Zinc and zinc alloy for negative electrode of primary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032248A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115733U (en) * | 1980-02-06 | 1981-09-04 | ||
| JPS61208751A (en) * | 1985-03-14 | 1986-09-17 | Fuji Elelctrochem Co Ltd | Dry cell |
| JPS62248118A (en) * | 1986-04-21 | 1987-10-29 | Toho Denshi Kogyo Kk | Test method for magnetic head or magnetic tape |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5066737A (en) * | 1973-10-18 | 1975-06-05 | ||
| JPS5098636A (en) * | 1974-12-13 | 1975-08-05 | ||
| JPS5371233A (en) * | 1976-12-06 | 1978-06-24 | Matsushita Electric Ind Co Ltd | Nickel zinc storage battery |
| JPS5825083A (en) * | 1981-07-22 | 1983-02-15 | ヴアルタ・バツテリ−・アクチエンゲゼルシヤフト | Zinc powder cathode not amalgamed for battery having alkaline electrolyte and method of producing same |
| JPS5875769A (en) * | 1981-10-30 | 1983-05-07 | Mitsui Mining & Smelting Co Ltd | Cathode active substance for cell |
-
1983
- 1983-08-01 JP JP58139494A patent/JPS6032248A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5066737A (en) * | 1973-10-18 | 1975-06-05 | ||
| JPS5098636A (en) * | 1974-12-13 | 1975-08-05 | ||
| JPS5371233A (en) * | 1976-12-06 | 1978-06-24 | Matsushita Electric Ind Co Ltd | Nickel zinc storage battery |
| JPS5825083A (en) * | 1981-07-22 | 1983-02-15 | ヴアルタ・バツテリ−・アクチエンゲゼルシヤフト | Zinc powder cathode not amalgamed for battery having alkaline electrolyte and method of producing same |
| JPS5875769A (en) * | 1981-10-30 | 1983-05-07 | Mitsui Mining & Smelting Co Ltd | Cathode active substance for cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115733U (en) * | 1980-02-06 | 1981-09-04 | ||
| JPS61208751A (en) * | 1985-03-14 | 1986-09-17 | Fuji Elelctrochem Co Ltd | Dry cell |
| JPS62248118A (en) * | 1986-04-21 | 1987-10-29 | Toho Denshi Kogyo Kk | Test method for magnetic head or magnetic tape |
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