JPS62154468A - Zinc alkaline battery - Google Patents

Zinc alkaline battery

Info

Publication number
JPS62154468A
JPS62154468A JP60292324A JP29232485A JPS62154468A JP S62154468 A JPS62154468 A JP S62154468A JP 60292324 A JP60292324 A JP 60292324A JP 29232485 A JP29232485 A JP 29232485A JP S62154468 A JPS62154468 A JP S62154468A
Authority
JP
Japan
Prior art keywords
zinc
negative electrode
hydrogen gas
alkaline
electrolyte
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
Application number
JP60292324A
Other languages
Japanese (ja)
Other versions
JPH0535548B2 (en
Inventor
Keiichi Kagawa
賀川　恵市
Hiroshi Hirahara
平原　弘
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.)
Mitsui Mining and Smelting Co Ltd
Original Assignee
Mitsui Mining and Smelting 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 Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to JP60292324A priority Critical patent/JPS62154468A/en
Publication of JPS62154468A publication Critical patent/JPS62154468A/en
Publication of JPH0535548B2 publication Critical patent/JPH0535548B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • 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

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE:To obtain a zinc alkaline battery whose hydrogen gas evolution from amalgamated or non-amalgamated zinc or zinc alloy used as a negative electrode is remarkably retarded by adding a specified amount of sulfolane as an inhibitor in an electrolyte comprising alkaline aqueous solution. CONSTITUTION:In a zinc alkaline battery using alkaline aqueous solution as an electrolyte and zinc or zinc alloy as a negative electrode, 0.2-5.0wt% sulfolane based on the alkaline aqueous solution is added to the electrolyte. Even when zinc alone is used as the negative electrode, the amount of hydrogen gas evolution is retarded. When zinc alloy containing one or more of lead, cadmium, indium, thallium, gallium, and aliminum is used as the negative elec trode, the effect is increased. When amalgamated zinc or amalgamated zinc alloy made of the zinc alloy is used, hydrogen gas evolution is furthermore decreased.

Description

【発明の詳細な説明】 し発明の属する分野］ 本発明は亜鉛アルカリ電池に関し、詳しくは電解液であ
るアルカリ水溶液に、インヒビターとしてスルホラン（
０４Ｈａ　ＳＯ２）［別名：テ１〜ラメチレンスル７オ
ンまたはテトラヒドロチオフェン−１，１−ダイオキサ
イド］を特定用添加することにより、水素ガス発生量を
著しく抑制した亜鉛アルカリ電池に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a zinc-alkaline battery, and more specifically, the present invention relates to a zinc-alkaline battery, and more specifically, to an aqueous alkaline solution as an electrolyte, sulfolane (
This invention relates to a zinc-alkaline battery in which the amount of hydrogen gas generated is significantly suppressed by the specific addition of 04Ha SO2) [also known as te1-ramethylenesul7one or tetrahydrothiophene-1,1-dioxide].

［発明の背景］ 単位型ω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
の負極材料として亜鉛が賞用されている。[Background of the Invention] Zinc is preferred as a negative electrode material for alkaline batteries because it has a large amount of electricity per unit type ω, is relatively chemically stable, has good processability, and is inexpensive.

しかし、電解液であるアルカリ水溶液〈アルカリ電解液
）の中では亜鉛の化学的溶解によって、電池内にガスが
蓄積して圧力がト冒し、電解液の漏出や電池の変形、甚
しいときには電池の破壊が起こることがある。その対策
として、従来では水銀の水素過電圧を利用した汞化亜鉛
が負極活物質として用いられている。ところが、最近で
は公害防止の観点から、電池の水銀含有けを（引力少な
くすることが社会的に要請されている。そのために、負
極亜鉛の水銀含有率を低下させたり、全く汞化していな
い亜鉛を負極に用い、かつ水素ガス発生特性等を低下さ
せないようにする研究が盛んになされている。例えば鉛
、インジウム、ガリウム等の元素を亜鉛に添加した亜鉛
合金を負極として用いる方法が提案されているが、この
ような亜鉛合金においても充分な特性を（ｑるためには
、水銀含有率は３％程度必要とし、未だ充分にはその出
が低減されていない。However, due to the chemical dissolution of zinc in the alkaline aqueous electrolyte (alkaline electrolyte), gas accumulates inside the battery, causing pressure to rise, leading to leakage of the electrolyte, deformation of the battery, and even serious damage to the battery. Destruction may occur. As a countermeasure against this, conventionally, zinc hydroxide, which utilizes the hydrogen overvoltage of mercury, has been used as a negative electrode active material. However, recently, from the perspective of pollution prevention, there has been a social demand to reduce the mercury content (attractive force) of batteries. There is active research being carried out on using zinc alloys as negative electrodes without degrading the hydrogen gas generation characteristics, etc.For example, a method has been proposed in which zinc alloys, in which elements such as lead, indium, and gallium are added to zinc, are used as negative electrodes. However, even in such a zinc alloy, in order to have sufficient properties, the mercury content must be about 3%, and mercury content has not yet been sufficiently reduced.

また、水素ガス発生のインヒビターとして有機物等を添
加する方法も提案されているが、未だ水素ガス発生の抑
制は不充分である。Furthermore, a method of adding an organic substance or the like as an inhibitor of hydrogen gas generation has been proposed, but the suppression of hydrogen gas generation is still insufficient.

［発明の目的］ 本発明は上記のような状況に鑑み、負極として用いられ
る汞化または無水化の亜鉛または亜鉛合金からの水素ガ
ス発生が著しく抑制した亜鉛アルカリ電池を提供するこ
とを目的とする。[Object of the invention] In view of the above-mentioned circumstances, an object of the present invention is to provide a zinc-alkaline battery in which hydrogen gas generation from anhydrous or anhydrous zinc or zinc alloy used as a negative electrode is significantly suppressed. .

［発明の経緯〕 本発明者は上記目的を達成するために、鋭意研究をした
ところ、アルカリ水溶液からなる電解液に、インヒビタ
ーとしてスルホランを特定量添加することにより、スル
ホランを無添加のものに比べて著しく水素ガス発生が抑
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 inventor conducted extensive research and found that by adding a specific amount of sulfolane as an inhibitor to an electrolytic solution consisting of an alkaline aqueous solution, the inventors found that the electrolyte solution, which is an alkaline aqueous solution, has a higher The present invention was based on the knowledge that hydrogen gas generation is significantly suppressed.

［発明の構成］ すなわら本発明は、アルカリ水溶液を電解液とし、負極
が亜鉛または亜鉛合金からなる亜鉛アルカリ電池におい
て、前記アルカリ水溶液に対して、スルホランを０．０
２〜５．０容量％添加したことを特徴とする亜鉛アルカ
リ電池にある。[Structure of the Invention] In other words, the present invention provides a zinc-alkaline battery in which an aqueous alkali solution is used as an electrolyte and a negative electrode is made of zinc or a zinc alloy.
There is a zinc-alkaline battery characterized in that 2 to 5.0% by volume of the zinc-alkaline battery is added.

本発明の亜鉛アルカリ電池においては、負極として亜鉛
単味を用いても水素ガス発生ｍが抑制され、また鉛、カ
ドミウム、インジウム、タリウム、ガリウム、アルミニ
ウム等の亜鉛の腐食を抑制する元素の少なくとも１種が
添加された亜鉛合金を負極として用いた場合にはさらに
良好な結果を示す。また、これら亜鉛または亜鉛合金を
汞化した汞化亜鉛または汞化亜鉛合金を用いた場合は当
然ながらさらに水素ガス発生歯が抑制される。In the zinc-alkaline battery of the present invention, hydrogen gas generation is suppressed even when zinc alone is used as the negative electrode, and at least one of elements such as lead, cadmium, indium, thallium, gallium, and aluminum that suppresses corrosion of zinc is suppressed. Even better results are shown when a seeded zinc alloy is used as the negative electrode. In addition, when a zinc oxide or a zinc oxide alloy obtained by converting these zinc or zinc alloys into oxides is used, hydrogen gas generation is naturally further suppressed.

スルホランの添加範囲は、電解液であるアルカリ水溶液
に対して０．０２〜５．０容量％が好ましく、０．０２
容聞％より小さい場合は添加効果が小さく、また５、０
容量％より大きい場合は水素ガス発生違の抑制には問題
ないが、容積的に活物質石を減らす必要があり、その分
電気量が小さくなる。このスルホランの添加効果につい
ては、明白ではないがスルホランの構造的なものまたは
イオウが水素ガス発生員を抑制するのに作用をもたらし
ているものと推定される。なお、本発明において、電解
液として用いられるアルカリ水溶液としては、水酸化カ
リウム溶液、水酸化ナトリウム溶液等が挙げられる。ま
たスルホランの添加方法については予め亜鉛粉中に添加
しておいても良く、また電解液またはゲル液中に添加し
ても全くさしつかえない。The addition range of sulfolane is preferably 0.02 to 5.0% by volume with respect to the alkaline aqueous solution as the electrolytic solution, and 0.02% by volume.
If it is less than 5%, the effect of addition is small, and 5,0
If it is larger than % by volume, there is no problem in suppressing hydrogen gas generation, but it is necessary to reduce the volume of active material stones, and the amount of electricity decreases accordingly. The effect of this addition of sulfolane is not clear, but it is presumed that the structure of sulfolane or sulfur has an effect on suppressing hydrogen gas generation. In the present invention, examples of the alkaline aqueous solution used as the electrolytic solution include potassium hydroxide solution and sodium hydroxide solution. Regarding the method of adding sulfolane, it may be added to the zinc powder in advance, or it may be added to the electrolytic solution or gel solution.

［発明の実施例］ 以下、本発明を実施例および比較例に基づき詳細に説明
するが、本発明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 described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

実施例１〜３０および比較例１〜１２ 負極として、第１表に示ず負極（１）〜（６）、すなわ
ちゲル化剤にてゲル状化した亜鉛粉、汞化亜鉛粉、亜鉛
合金粉、汞化亜鉛合金粉をそれぞれ用い、正極に二酸化
マンガンと導電剤を混合したもの、電解液として４０　
ｗｔ、％水酸化カリウム溶液に酸化亜鉛を飽和させたも
の、またはこれにスルホランを第１表に示す割合で添加
したものを各々使用し、第１図に示す市販の電池（ＬＲ
−６）の構成に近似させたアルカリマンガン電池を用い
て試験を行なった。Examples 1 to 30 and Comparative Examples 1 to 12 As negative electrodes, negative electrodes (1) to (6) not shown in Table 1, that is, zinc powder gelled with a gelling agent, zinc chloride powder, and zinc alloy powder , zinc alloy powder mixed with manganese dioxide and a conductive agent as the positive electrode, and 40% as the electrolyte.
A commercially available battery (LR
Tests were conducted using an alkaline manganese battery with a configuration similar to -6).

第１図のアルカリマンガン電池は、正極缶１、正極２、
セパレーター３、負極（ゲル状化した亜鉛粉、汞化亜鉛
粉、亜鉛合金粉、汞化亜鉛合金粉）４、負極集電体５、
パツキン６、押さえ板７で構成されている。The alkaline manganese battery shown in Figure 1 consists of a positive electrode can 1, a positive electrode 2,
Separator 3, negative electrode (gelled zinc powder, zinc powder, zinc alloy powder, zinc alloy powder) 4, negative electrode current collector 5,
It is composed of a packing 6 and a pressing plate 7.

この電池を負極の種類、スルホラン添加ｒを変えて各々
１０個ずつ電池を組立て、６０℃×　１ケ月保存し、そ
の時の電池内の水素ガス発生ｆｆ１（ｃｃ）を測定し、
各々１０個の測定結果の平均値を第１表に示した。Assemble 10 batteries each with different types of negative electrode and sulfolane addition r, store them at 60°C for 1 month, and measure hydrogen gas generation ff1 (cc) in the batteries at that time.
Table 1 shows the average values of the 10 measurement results.

第１表 ：ｌ：１：１０回測定の平均値、＊２：亜鉛粉を使用、
＊３：亜鉛粉を１．０％ＨＯで水化したものを使用、＊
４：亜鉛−鉛（０，０５％）−インジウム（０，０２％
）合金粉使用。Table 1: l:1: Average value of 10 measurements, *2: Using zinc powder,
*3: Use zinc powder hydrated with 1.0% HO, *
4: Zinc-Lead (0.05%)-Indium (0.02%
) Uses alloy powder.

第　　１　　表（続き） （０，０２％）合金粉を１．０％Ｈｇで水化したちのを
使用、＊Ｇ：亜鉛−鉛（０，０５％）−アルミニウム（
Ｏ，ＯＳ％）−インジウム＜０．０２％）合金粉使用、
＊７：亜鉛−鉛（０，０５％）−アルミニウム（Ｏ，Ｏ
Ｓ％）−インジウム（０，０２％）合金粉を１．０％Ｈ
ｇで水化したものを使用。Table 1 (Continued) (0.02%) Alloy powder hydrated with 1.0%Hg was used, *G: Zinc-Lead (0.05%)-Aluminum (
O,OS%)-indium<0.02%) alloy powder used,
*7: Zinc-lead (0.05%)-aluminum (O, O
S%)-indium (0.02%) alloy powder to 1.0%H
Use the one hydrated with g.

第１表に示されるごとく、スルホランを０．０２〜５．
０容量％の範囲で添加した実施例１〜３０は、スルホラ
ンを全く添加しない実施例１〜１２に比べて負極の種類
（負極（１）〜（６））に関係なく、水素ガス発生間を
著しく抑制していることがわかる。As shown in Table 1, sulfolane was added in a range of 0.02 to 5.
Examples 1 to 30, in which sulfolane was added in the range of 0% by volume, had a shorter time between hydrogen gas generation, regardless of the type of negative electrode (negative electrodes (1) to (6)), compared to Examples 1 to 12, in which sulfolane was not added at all. It can be seen that it is significantly suppressed.

なお、本実施例および比較例では電解液として水酸化カ
リウム水溶液を用いたが、水酸化ナトリウム水溶液で実
施しても同様な結果が得られた。Although a potassium hydroxide aqueous solution was used as the electrolyte in the present example and comparative example, similar results were obtained even when a sodium hydroxide aqueous solution was used.

［発明の効果１ 以上説明のように、電解液であるアルカリ水溶液に、特
定量のスルホランを添加する本発明の伊鉛アルカリ電池
によれば、負極として低水化亜鉛粉あるいは無汞化亜鉛
粉を使用した場合においても、電池内で発生する水素ガ
ス量を大幅に低減化でき、工業的価値が大である。[Effect of the invention 1 As explained above, according to the lead-acid alkaline battery of the present invention in which a specific amount of sulfolane is added to the alkaline aqueous solution as the electrolyte, low hydration zinc powder or non-hydration zinc powder is used as the negative electrode. Even when using this method, the amount of hydrogen gas generated within the battery can be significantly reduced, which is of great industrial value.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明に係わるアルカリマンガン電池の原理図
を示す。 １：正極ζｂ、　２：正極、　３：セパレーター、４：
負極、　５：負極集電体、　６：パツキン、７：押さえ
板。 特許出願人　三井金属鉱業株式会社 代即人　　弁理士　伊東辰雄FIG. 1 shows a principle diagram of an alkaline manganese battery according to the present invention. 1: Positive electrode ζb, 2: Positive electrode, 3: Separator, 4:
Negative electrode, 5: negative electrode current collector, 6: packing, 7: holding plate. Patent applicant: Mitsui Mining & Mining Co., Ltd. Patent attorney: Tatsuo Ito

Claims (1)

【特許請求の範囲】 １、アルカリ水溶液を電解液とし、負極が亜鉛または亜
鉛合金からなる亜鉛アルカリ電池において、前記アルカ
リ水溶液に対して、スルホランを０．０２〜５．０容量
％添加したことを特徴とする亜鉛アルカリ電池。 ２、前記亜鉛合金が鉛、カドミウム、インジウム、タリ
ウム、ガリウム、アルミニウムの少なくとも１種を含有
する前記特許請求の範囲第１項記載の亜鉛アルカリ電池
。 ３、前記亜鉛または亜鉛合金が汞化されている前記特許
請求の範囲第１項または第２項記載の亜鉛アルカリ電池
。[Claims] 1. In a zinc-alkaline battery in which an aqueous alkaline solution is used as an electrolyte and a negative electrode is made of zinc or a zinc alloy, 0.02 to 5.0% by volume of sulfolane is added to the aqueous alkaline solution. Features: Zinc alkaline battery. 2. The zinc-alkaline battery according to claim 1, wherein the zinc alloy contains at least one of lead, cadmium, indium, thallium, gallium, and aluminum. 3. The zinc-alkaline battery according to claim 1 or 2, wherein the zinc or zinc alloy is hydrogenated.
JP60292324A 1985-12-26 1985-12-26 Zinc alkaline battery Granted JPS62154468A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60292324A JPS62154468A (en) 1985-12-26 1985-12-26 Zinc alkaline battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60292324A JPS62154468A (en) 1985-12-26 1985-12-26 Zinc alkaline battery

Publications (2)

Publication Number Publication Date
JPS62154468A true JPS62154468A (en) 1987-07-09
JPH0535548B2 JPH0535548B2 (en) 1993-05-26

Family

ID=17780305

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60292324A Granted JPS62154468A (en) 1985-12-26 1985-12-26 Zinc alkaline battery

Country Status (1)

Country Link
JP (1) JPS62154468A (en)

Also Published As

Publication number Publication date
JPH0535548B2 (en) 1993-05-26

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