JPH05135776A - Cylindrical alkaline battery - Google Patents
Cylindrical alkaline batteryInfo
- Publication number
- JPH05135776A JPH05135776A JP3326574A JP32657491A JPH05135776A JP H05135776 A JPH05135776 A JP H05135776A JP 3326574 A JP3326574 A JP 3326574A JP 32657491 A JP32657491 A JP 32657491A JP H05135776 A JPH05135776 A JP H05135776A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- negative electrode
- current collector
- weight
- electrode current
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、負極活物質として無水
銀の亜鉛を用いる筒形アルカリ電池に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cylindrical alkaline battery using anhydrous zinc as a negative electrode active material.
【０００２】[0002]
【従来の技術】負極活物質として亜鉛を用いる筒形アル
カリ電池では、亜鉛の腐食による水素ガスの発生を抑制
するために、亜鉛粒子の表面を水銀でアマルガム化する
ことが行われていた。そして、その水銀量は、亜鉛に対
する腐食抑制効果を重視して、多い場合、アマルガム化
率（汞化率）で１０重量％近くまでに達していた（たと
えば、「新しい電池」、東京電機大学出版局発行、昭和
５３年、第４２頁）。2. Description of the Related Art In a cylindrical alkaline battery using zinc as a negative electrode active material, the surface of zinc particles is amalgamated with mercury in order to suppress generation of hydrogen gas due to corrosion of zinc. And, the amount of mercury reached about 10% by weight in terms of amalgamation rate (degradation rate) in many cases with emphasis on the corrosion inhibition effect on zinc (for example, "new battery", published by Tokyo Denki University Press). Issued by the Bureau, 1978, p. 42).
【０００３】しかしながら、最近は水銀による環境汚染
が問題になり、アマルガム化率を減少させることが要求
されている。However, recently, environmental pollution due to mercury has become a problem, and it is required to reduce the amalgamation rate.
【０００４】そのため、水銀に代えて、インジウム、
鉛、ガリウム、アルミニウム、ビスマスなどを亜鉛に添
加して、亜鉛と合金化することによって亜鉛の腐食を抑
制することが検討され、現在では、アマルガム化率を
０．１０〜０．１５重量％程度にまで低減できるように
なってきた。Therefore, instead of mercury, indium,
It has been investigated to suppress corrosion of zinc by adding lead, gallium, aluminum, bismuth, etc. to zinc and alloying with zinc. Currently, the amalgamation rate is about 0.10 to 0.15% by weight. It has become possible to reduce to
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、今後、
無水銀化していくためには、これまで提案されてきた添
加金属だけでは充分といえず、また、従来から腐食抑制
剤として提案されているラクトニトリルやカルバゾール
などの有機系インヒビターも、充分な効果を持つものが
なく、無水銀化のための有効な手段となっていないのが
現状である。[Problems to be Solved by the Invention] However, in the future,
In order to eliminate mercury, the additive metals that have been proposed so far cannot be said to be sufficient, and organic inhibitors such as lactonitrile and carbazole that have been conventionally proposed as corrosion inhibitors have sufficient effects. In the present situation, there is no such thing as, and it is not an effective means for silver-free conversion.
【０００６】したがって、本発明は、負極活物質として
無水銀の亜鉛を用いる筒形アルカリ電池において、環境
汚染を引き起こすことなく、亜鉛の腐食を抑制して、亜
鉛からの水素ガスの発生を抑制することを第１の目的と
する。Therefore, according to the present invention, in a cylindrical alkaline battery using anhydrous zinc as a negative electrode active material, corrosion of zinc is suppressed and generation of hydrogen gas from zinc is suppressed without causing environmental pollution. This is the first purpose.
【０００７】また、無水銀の亜鉛を負極活物質として用
いる筒形アルカリ電池では、上記のような亜鉛からの水
素ガスの発生以外にも、従来はあまり問題になることが
なかった負極集電体と亜鉛との接触部からの水素ガスの
発生という新たな問題が生じる。In addition, in the cylindrical alkaline battery using zinc of anhydrous silver as the negative electrode active material, in addition to the above-described generation of hydrogen gas from zinc, the negative electrode current collector has not been so much a problem in the past. A new problem arises that hydrogen gas is generated from the contact area between zinc and zinc.
【０００８】すなわち、筒形アルカリ電池においては、
負極集電体に関し、真鍮が導電性が高く、かつ強度があ
り、しかも他の高導電体に比べて安価であるという理由
から、真鍮製のものが使用されているが、無水銀化に伴
って、この真鍮製の負極集電体と亜鉛との接触部から水
素ガスが発生するのである。That is, in the cylindrical alkaline battery,
Regarding the negative electrode current collector, brass is used because it has high conductivity and strength, and it is cheaper than other high conductors. Then, hydrogen gas is generated from the contact portion between the brass negative electrode current collector and zinc.
【０００９】つまり、従来のように、亜鉛の腐食抑制の
ために水銀が使用されている場合には、負極集電体を負
極剤中に浸漬すると、負極集電体の表面は亜鉛でメッキ
されると共に水銀でアマルガム化されるので、負極集電
体からの水素ガスの発生がほとんど生じなかった。That is, in the conventional case where mercury is used to suppress corrosion of zinc, when the negative electrode current collector is dipped in the negative electrode agent, the surface of the negative electrode current collector is plated with zinc. At the same time, since it is converted to amalgam with mercury, almost no hydrogen gas is generated from the negative electrode current collector.
【００１０】しかし、水銀を使用しない電池では、水銀
によるアルガム化がないため、負極集電体を負極剤中に
浸漬した場合に亜鉛メッキされにくい部分、たとえば、
負極集電体の先端や、負極剤中から抜け出る部分などの
亜鉛メッキがされにくい部分と亜鉛との接触部から水素
ガスが発生するのである。However, in a battery that does not use mercury, since there is no agglomeration by mercury, a portion which is difficult to be galvanized when the negative electrode current collector is immersed in the negative electrode agent, for example,
Hydrogen gas is generated from the tip of the negative electrode current collector and the contact portion between zinc and a portion that is difficult to be galvanized, such as a portion coming out of the negative electrode agent.
【００１１】したがって、本発明は、この負極集電体と
亜鉛との接触部からの水素ガスの発生を抑制することを
第２の目的をする。Therefore, a second object of the present invention is to suppress the generation of hydrogen gas from the contact portion between the negative electrode current collector and zinc.
【００１２】さらに、無水銀の亜鉛を負極活物質として
用いる筒形アルカリ電池では、保存による重負荷特性の
低下という問題も発生する。[0012] Further, in a cylindrical alkaline battery in which zinc of anhydrous silver is used as a negative electrode active material, there is a problem that heavy load characteristics are deteriorated by storage.
【００１３】したがって、本発明は、この保存による重
負荷特性の低下を抑制することを第３の目的とする。Therefore, a third object of the present invention is to suppress the deterioration of the heavy load characteristic due to the storage.
【００１４】[0014]
【課題を解決するための手段】本発明は、亜鉛の腐食抑
制剤としてリチウム塩を電解液に添加し、負極集電体の
表面を亜鉛、スズ（錫）および鉛よりなる群から選ばれ
た少なくとも１種の金属でメッキし、かつ電解液中の水
酸化カリウムの濃度を３５〜４５重量％にし、酸化亜鉛
の濃度を３〜７重量％に特定することによって、上記目
的を達成したのである。According to the present invention, a lithium salt as a corrosion inhibitor for zinc is added to an electrolytic solution, and the surface of a negative electrode current collector is selected from the group consisting of zinc, tin and lead. The above object was achieved by plating with at least one metal, and specifying the concentration of potassium hydroxide in the electrolytic solution to 35 to 45% by weight and the concentration of zinc oxide to 3 to 7% by weight. ..
【００１５】すなわち、電解液へのリチウム塩の添加に
よって、亜鉛の腐食を抑制して亜鉛からの水素ガスの発
生を抑制するとともに、負極集電体の表面を上記特定の
金属でメッキすることによって、負極集電体と亜鉛との
接触部からの水素ガスの発生を抑制し、電解液中の水酸
化カリウムや酸化亜鉛の濃度を上記のように特定するこ
とによって、保存による重負荷特性の低下を抑制したの
である。That is, by adding a lithium salt to the electrolytic solution, the corrosion of zinc is suppressed and the generation of hydrogen gas from zinc is suppressed, and the surface of the negative electrode current collector is plated with the above-mentioned specific metal. By suppressing the generation of hydrogen gas from the contact area between the negative electrode current collector and zinc and specifying the concentrations of potassium hydroxide and zinc oxide in the electrolyte as described above, the heavy load characteristics are reduced by storage. Was suppressed.
【００１６】つぎに、本発明の各構成要件について詳細
に説明する。Next, each constituent element of the present invention will be described in detail.
【００１７】リチウム塩としては、たとえば、水酸化リ
チウム、炭酸リチウム、リン酸リチウム、ケイ酸リチウ
ムなどが用いられる。特に水酸化リチウムは、水酸イオ
ン（ＯＨ- ）が電池に悪影響を及ぼさないので、本発明
におけるリチウム塩として好適に用いられる。As the lithium salt, for example, lithium hydroxide, lithium carbonate, lithium phosphate, lithium silicate or the like is used. In particular, lithium hydroxide is preferably used as the lithium salt in the present invention because hydroxide ion (OH − ) does not adversely affect the battery.
【００１８】上記のリチウム塩は、電解液に添加する
と、電解液中に溶解してリチウムイオンとして存在する
ようになる。When the above lithium salt is added to the electrolytic solution, it will be dissolved in the electrolytic solution and will exist as lithium ions.
【００１９】電解液中のリチウムイオンが亜鉛の腐食を
抑制し、亜鉛からの水素ガスの発生を抑制する理由は、
現在のところ必ずしも明確ではないが、リチウムイオン
が亜鉛イオンの溶出を抑制し、それによって亜鉛からの
水素ガスの発生を抑制するものと考えられる。The reason why lithium ions in the electrolytic solution suppress corrosion of zinc and suppress generation of hydrogen gas from zinc is as follows.
Although not clear at present, it is considered that lithium ions suppress the elution of zinc ions and thereby suppress the generation of hydrogen gas from zinc.
【００２０】リチウム塩の電解液への添加量としては、
亜鉛に対して０．０５〜１０重量％、特に０．１〜５重
量％が好ましい。The amount of lithium salt added to the electrolytic solution is
It is preferably 0.05 to 10% by weight, particularly 0.1 to 5% by weight, based on zinc.
【００２１】リチウム塩の電解液への添加量が亜鉛に対
して０．０５重量％より少ない場合は、亜鉛の腐食を抑
制して亜鉛からの水素ガスの発生を抑制する効果が充分
に発揮されず、またリチウム塩の電解液への添加量が亜
鉛に対して１０重量％より多くなると、リチウムイオン
が二酸化マンガンなどの正極活物質の表面に吸着して、
放電特性を低下させるおそれある。When the amount of the lithium salt added to the electrolytic solution is less than 0.05% by weight with respect to zinc, the effect of suppressing corrosion of zinc and suppressing generation of hydrogen gas from zinc is sufficiently exerted. If the amount of lithium salt added to the electrolytic solution exceeds 10% by weight with respect to zinc, lithium ions are adsorbed on the surface of the positive electrode active material such as manganese dioxide,
The discharge characteristics may be deteriorated.
【００２２】本発明では、負極集電体の表面を亜鉛、ス
ズおよび鉛よりなる群から選ばれた少なくとも１種の金
属でメッキすることによって、負極集電体と亜鉛との接
触部からの水素ガスの発生を抑制するが、これについて
詳しく説明すると、次の通りである。In the present invention, the surface of the negative electrode current collector is plated with at least one metal selected from the group consisting of zinc, tin and lead, so that hydrogen from the contact portion between the negative electrode current collector and zinc is plated. The generation of gas is suppressed, which will be described in detail below.
【００２３】まず、亜鉛でメッキした場合について説明
すると、負極集電体の表面を亜鉛でメッキしておくと、
負極集電体の素材である真鍮の露出部分がなくなるた
め、負極集電体と亜鉛との接触部からの水素がスの発生
が抑制される。First, the case of plating with zinc will be explained. When the surface of the negative electrode current collector is plated with zinc,
Since the exposed portion of brass, which is the material of the negative electrode current collector, is eliminated, generation of hydrogen gas from the contact portion between the negative electrode current collector and zinc is suppressed.
【００２４】また、負極集電体の表面をスズまたは鉛で
メッキしておくと、スズや鉛は亜鉛よりイオン傾向が小
さいので、負極集電体を負極剤中に浸漬したときに亜鉛
と置換することがなく、したがって、負極集電体の素材
である真鍮の露出部分が生じない。そして、これらのス
ズや鉛は真鍮よりもイオン化傾向が小さく、水素過電圧
が高いので、負極集電体と亜鉛との接触部からの水素ガ
スの発生が抑制されることになる。When the surface of the negative electrode current collector is plated with tin or lead, tin and lead have a smaller ionic tendency than zinc, so that the negative electrode current collector is replaced with zinc when immersed in the negative electrode agent. Therefore, the exposed portion of brass, which is the material of the negative electrode current collector, does not occur. Since tin and lead have a smaller ionization tendency and higher hydrogen overvoltage than brass, generation of hydrogen gas from the contact portion between the negative electrode current collector and zinc is suppressed.
【００２５】もとより、亜鉛、スズおよび鉛をたとえば
合金化することなどによって２種以上組み合わせて用い
てもよい。Of course, zinc, tin, and lead may be used in combination of two or more by alloying, for example.
【００２６】負極集電体の表面へのメッキ方法として
は、電解メッキ、無電解メッキのいずれも採用できる。
メッキの厚みは、均一なメッキが得られればいくらでも
よいが、通常は２〜１０μｍ程度にされる。ただし、こ
のメッキ厚みの測定は、通常、負極集電体の長さ方向の
中央部付近で行われる。As a method for plating the surface of the negative electrode current collector, either electrolytic plating or electroless plating can be adopted.
The thickness of the plating may be any number as long as uniform plating can be obtained, but it is usually about 2 to 10 μm. However, this plating thickness is usually measured near the center of the negative electrode current collector in the longitudinal direction.
【００２７】つぎに、保存による重負荷特性の低下およ
びその抑制について詳しく説明する。Next, the deterioration of heavy load characteristics due to storage and its suppression will be described in detail.
【００２８】無水銀の亜鉛を負極活物質として用いた筒
形アルカリ電池では、従来の水銀を用いていた筒形アル
カリ電池に比べて、保存による重負荷特性の低下が大き
くなる。In a cylindrical alkaline battery using zinc anhydrous zinc as a negative electrode active material, the heavy load characteristic due to storage is greatly reduced as compared with a conventional cylindrical alkaline battery using mercury.
【００２９】これは、電解液中の水酸化カリウムや酸化
亜鉛の濃度が低いと保存中に亜鉛表面に酸化物ができや
すく、これが保存後の放電に悪影響を与えるためである
と考えられる。It is considered that this is because when the concentration of potassium hydroxide or zinc oxide in the electrolytic solution is low, oxides are easily formed on the zinc surface during storage, which adversely affects the discharge after storage.
【００３０】本発明では、この保存による重負荷特性の
低下を電解液中の水酸化カリウムや酸化亜鉛の濃度を特
定することによって、抑制するのである。In the present invention, the deterioration of the heavy load characteristic due to this storage is suppressed by specifying the concentrations of potassium hydroxide and zinc oxide in the electrolytic solution.
【００３１】すなわち、本発明では、電解液中の水酸化
カリウムの濃度を３５〜４５重量％、特に３７〜４２重
量％にし、酸化亜鉛の濃度を３〜７重量％、特に５重量
％以上にすることによって、保存による重負荷特性の低
下を抑制するのである。That is, in the present invention, the concentration of potassium hydroxide in the electrolytic solution is 35 to 45% by weight, particularly 37 to 42% by weight, and the concentration of zinc oxide is 3 to 7% by weight, especially 5% by weight or more. By doing so, the deterioration of the heavy load characteristics due to storage is suppressed.
【００３２】保存による重負荷特性の低下抑制という面
からは、水酸化カリウム濃度をさらに高くしてもよい
が、水酸化カリウムの濃度が高すぎると放電電圧が低く
なり、所定電圧（通常、この種の電池では０．９Ｖ）ま
での放電持続時間が短くなるので、前記のように、水酸
化カリウムの濃度の上限は４５重量％にするのが適切で
ある。From the viewpoint of suppressing deterioration of heavy load characteristics due to storage, the concentration of potassium hydroxide may be further increased. However, if the concentration of potassium hydroxide is too high, the discharge voltage will be lowered and a predetermined voltage (usually Since the discharge duration of up to 0.9 V) is shortened in the case of the type B battery, it is appropriate that the upper limit of the concentration of potassium hydroxide is 45% by weight, as described above.
【００３３】また同様に、保存による重負荷特性の低下
抑制という面からは、酸化亜鉛の濃度をさらに高くして
もよいが、酸化亜鉛の濃度が７重量％を超えると、亜鉛
の溶解などにより酸化亜鉛の濃度が少し増加しただけで
も、沈澱物が生じ、その沈澱物が亜鉛の腐食を助長する
傾向があるため、その上限は７重量％にするのが好まし
い。Similarly, from the viewpoint of suppressing the deterioration of heavy load characteristics due to storage, the concentration of zinc oxide may be further increased. However, when the concentration of zinc oxide exceeds 7% by weight, it may be dissolved by zinc. Even if the concentration of zinc oxide is slightly increased, a precipitate is generated, and the precipitate tends to promote the corrosion of zinc. Therefore, the upper limit is preferably 7% by weight.
【００３４】本発明においては、上記のようにリチウム
塩を電解液に添加し、負極集電体の表面を特定の金属で
メッキし、電解液中の水酸化カリウムや酸化亜鉛の濃度
を特定の濃度にすることに特徴があるが、それ以外は従
来と同様の構成を採用することができる。In the present invention, the lithium salt is added to the electrolytic solution as described above, the surface of the negative electrode current collector is plated with a specific metal, and the concentration of potassium hydroxide or zinc oxide in the electrolytic solution is specified. Although it is characterized in that the concentration is set, the same configuration as the conventional one can be adopted except for the above.
【００３５】たとえば、負極活物質としての亜鉛には、
亜鉛そのものはもとより、亜鉛にインジウム、鉛、ガリ
ウム、アルミニウム、ビスマスなどを添加したものも用
いることができるし、正極活物質としては、たとえば二
酸化マンガンなどを用いることができる。For example, for zinc as the negative electrode active material,
Not only zinc itself, but also zinc added with indium, lead, gallium, aluminum, bismuth, or the like can be used, and as the positive electrode active material, for example, manganese dioxide or the like can be used.
【００３６】[0036]
【実施例】つぎに、実施例をあげて本発明をより具体的
に説明する。なお、実施例に先立ち、電解液中へのリチ
ウム塩の添加による亜鉛からの水素ガスの発生抑制効果
および負極集電体の表面へのメッキによる負極集電体と
亜鉛との接触部からの水素ガスの発生抑制効果ならびに
リチウム塩の添加が放電持続時間に与える影響を実験例
１で明らかにする。EXAMPLES Next, the present invention will be described more specifically by way of examples. Incidentally, prior to the examples, the effect of suppressing the generation of hydrogen gas from zinc by the addition of a lithium salt to the electrolytic solution and the hydrogen from the contact portion between the negative electrode current collector and zinc by plating on the surface of the negative electrode current collector. Experimental Example 1 clarifies the effect of suppressing the generation of gas and the effect of the addition of lithium salt on the discharge duration.
【００３７】実験例１ 水酸化カリウムの濃度が３５重量％、酸化亜鉛の濃度が
５．５重量％のアルカリ水溶液を電解液として用い、こ
の電解液にリチウム塩として水酸化リチウムを各種添加
量で添加し、また真鍮製の負極集電体へのメッキの種類
を変えて、図１に示す構造の単３形アルカリ電池を作製
した。Experimental Example 1 An alkaline aqueous solution having a potassium hydroxide concentration of 35% by weight and a zinc oxide concentration of 5.5% by weight was used as an electrolytic solution, and lithium hydroxide as a lithium salt was added to the electrolytic solution at various addition amounts. AA alkaline batteries having the structure shown in FIG. 1 were prepared by adding and changing the type of plating on the brass negative electrode current collector.
【００３８】図１に示す電池について説明すると、図
中、１は正極合剤であり、この正極合剤１は二酸化マン
ガンを正極活物質とし、これに導電助剤としてのリン状
黒鉛とバインダーとしてのポリアクリル酸ソーダを加え
て混合した合剤をリング状に成形して、端子付きの正極
缶２内に挿入したものである。The battery shown in FIG. 1 will be described. In the figure, 1 is a positive electrode mixture, and this positive electrode mixture 1 uses manganese dioxide as a positive electrode active material, and phosphorous graphite as a conductive additive and a binder. The mixed material obtained by adding and mixing the above sodium polyacrylate is molded into a ring shape and inserted into the positive electrode can 2 with a terminal.
【００３９】３はセパレータであり、４はペースト状亜
鉛からなる負極剤である。この負極剤４は、ビスマス、
インジウムおよび鉛を含有した粒度３５〜１５０メッシ
ュの亜鉛粉末６０重量部とポリアクリル酸ソーダ２重量
部を乾式混合した後、電解液３８重量部を加えて攪拌
し、ゲル化させて、ペースト状に調製したものである。Reference numeral 3 is a separator, and 4 is a negative electrode agent made of paste zinc. The negative electrode agent 4 is bismuth,
After 60 parts by weight of zinc powder containing indium and lead and having a particle size of 35 to 150 mesh and 2 parts by weight of sodium polyacrylate are dry-mixed, 38 parts by weight of an electrolytic solution is added, and the mixture is stirred and gelled to form a paste. It was prepared.
【００４０】５は負極集電体、６は封口体、７は金属ワ
ッシャ、８は樹脂ワッシャ、９は絶縁キャップ、１０は
負極端子板、１１は樹脂外装体であり、封口体６には図
示していないが電池破裂防止用の薄肉部が設けられてい
る。Reference numeral 5 is a negative electrode current collector, 6 is a sealing body, 7 is a metal washer, 8 is a resin washer, 9 is an insulating cap, 10 is a negative electrode terminal plate, 11 is a resin exterior body, and the sealing body 6 is a figure. Although not shown, a thin portion is provided to prevent the battery from bursting.
【００４１】この電池における亜鉛の充填量は３．５ｇ
で、電解液量は２ｍｌであり、上記負極集電体５は、真
鍮製で、全長が３０ｍｍ、その軸部の直径が１．５ｍｍ
であり、封口体６の透孔に挿入され、その先端から約２
０ｍｍの長さにわたって負極剤４中に浸漬され、他方の
端部は負極端子板１０に溶接されている。The zinc filling amount in this battery was 3.5 g.
The amount of electrolyte is 2 ml, and the negative electrode current collector 5 is made of brass and has a total length of 30 mm and a shaft portion diameter of 1.5 mm.
And is inserted into the through hole of the sealing body 6 and about 2 from the tip thereof.
It is dipped in the negative electrode agent 4 over a length of 0 mm, and the other end is welded to the negative electrode terminal plate 10.
【００４２】そして、上記電解液には水酸化リチウムが
各種添加量で添加されており（ただし、比較のため、無
添加のものもある）、負極集電体５の表面は各種金属で
メッキされている（ただし、比較のため、メッキしてい
ないものもある）。Lithium hydroxide is added to the above-mentioned electrolytic solution in various addition amounts (however, for comparison, some are not added), and the surface of the negative electrode current collector 5 is plated with various metals. (However, for comparison, some are not plated).
【００４３】それぞれの電池を６０℃で４０日間保存
し、水素ガスの発生量を測定した。また、それぞれの電
池について１０Ω連続放電を行ない、その放電持続時間
を測定した。その結果を表１〜表３に示す。ガス発生量
測定用の電池については、封口体６の薄肉部（いわゆ
る、ベント部）にあらかじめ穴をあけておいた。Each battery was stored at 60 ° C. for 40 days, and the amount of hydrogen gas generated was measured. Further, each battery was continuously discharged at 10Ω and the discharge duration time was measured. The results are shown in Tables 1 to 3. Regarding the battery for measuring the gas generation amount, a hole was previously made in the thin portion (so-called vent portion) of the sealing body 6.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【表３】 [Table 3]
【００４７】表１〜表３に示す結果からわかるように、
水素ガスの発生抑制という面からは、水酸化リチウムの
添加量（ただし、亜鉛に対する重量％、以下同様）は
０．０５重量％以上が好ましく、特に０．２重量％以上
が好ましい。また、放電特性面からは、水酸化リチウム
の添加量が５重量％を超えると放電持続時間が短くなる
ので、実用上、水酸化リチウムの添加量は０．０５〜５
重量％が好ましく、水素ガスの発生抑制という面を考慮
すると、特に０．１〜５重量％、とりわけ０．２重量％
前後が好ましいといえる。As can be seen from the results shown in Tables 1 to 3,
From the viewpoint of suppressing the generation of hydrogen gas, the amount of lithium hydroxide added (however,% by weight relative to zinc, the same applies hereinafter) is preferably 0.05% by weight or more, and particularly preferably 0.2% by weight or more. Further, from the viewpoint of discharge characteristics, when the amount of lithium hydroxide added exceeds 5% by weight, the discharge duration becomes short, so in practice, the amount of lithium hydroxide added is 0.05 to 5%.
% Is preferable, and considering the aspect of suppressing the generation of hydrogen gas, 0.1 to 5% by weight, particularly 0.2% by weight is particularly preferable.
It can be said that the front and back are preferable.
【００４８】負極集電体のメッキについては、亜鉛メッ
キ、スズメッキ、鉛メッキ、鉛−スズ合金メッキ（半田
メッキ）のいずれも水素ガスの発生抑制効果があるが、
ガス発生の抑制効果は亜鉛メッキ、スズメッキ、鉛メッ
キ、鉛−スズ合金メッキの順に大きくなり、特に鉛メッ
キ、鉛−スズ合金メッキが効果が大きかった。Regarding the plating of the negative electrode current collector, any of zinc plating, tin plating, lead plating, and lead-tin alloy plating (solder plating) has an effect of suppressing generation of hydrogen gas.
The effect of suppressing gas generation increased in the order of zinc plating, tin plating, lead plating, and lead-tin alloy plating, and lead plating and lead-tin alloy plating were particularly effective.
【００４９】実施例１〜１２および比較例１〜１２ 亜鉛粉末としてビスマス、インジウムおよび鉛を含有し
た無水銀の亜鉛を用い、電解液には水酸化リチウムを亜
鉛に対して０．２重量％添加し、負極集電体には表面を
鉛−スズ合金でメッキした真鍮製の負極集電体を用い、
電解液中の水酸化カリウムおよび酸化亜鉛の濃度を種々
に変えて、図１と同様の構造の単３形アルカリ電池を作
製した。Examples 1 to 12 and Comparative Examples 1 to 12 Zinc-free zinc containing bismuth, indium and lead was used as zinc powder, and lithium hydroxide was added to the electrolytic solution in an amount of 0.2% by weight based on zinc. Then, as the negative electrode current collector, a brass negative electrode current collector whose surface is plated with lead-tin alloy is used.
AA alkaline batteries having the same structure as in FIG. 1 were prepared by changing the concentrations of potassium hydroxide and zinc oxide in the electrolytic solution.
【００５０】得られた電池を、初度および６０℃で２０
日間保存後に、それぞれ２０℃で負荷５Ωの連続放電を
行い、放電容量を測定し、初度放電容量に対する保存後
の放電容量の保持率を求めた。その結果を表４〜表５に
示す。The obtained battery was tested at the initial temperature and 60 ° C. for 20 minutes.
After storage for a day, continuous discharge with a load of 5Ω was performed at 20 ° C., the discharge capacity was measured, and the retention rate of the discharge capacity after storage with respect to the initial discharge capacity was determined. The results are shown in Tables 4-5.
【００５１】[0051]
【表４】 [Table 4]
【００５２】[0052]
【表５】 [Table 5]
【００５３】表４〜表５に示す結果からわかるように、
電解液中の水酸化カリウムの濃度が３５重量％以上、特
に３７重量％以上で、かつ酸化亜鉛の濃度が３重量％以
上、特に５重量％以上で好ましい結果が得られる。As can be seen from the results shown in Tables 4 to 5,
Preferable results are obtained when the concentration of potassium hydroxide in the electrolytic solution is 35% by weight or more, particularly 37% by weight or more, and the concentration of zinc oxide is 3% by weight or more, particularly 5% by weight or more.
【００５４】[0054]
【発明の効果】以上説明したように、本発明では、亜鉛
の腐食抑制剤としてリチウム塩を電解液に添加すること
によって、亜鉛の腐食を抑制して亜鉛からの水素ガスの
発生を抑制するとともに、負極集電体の表面を亜鉛、ス
ズおよび鉛よりなる群から選ばれた少なくとも１種の金
属でメッキすることによって、負極集電体と亜鉛との接
触部からの水素ガスの発生を抑制し、かつ電解液中の水
酸化カリウムの濃度を３５〜４５重量％、特に３７〜４
２重量％にし、酸化亜鉛の濃度を３〜７重量％、特に５
重量％以上にすることによって、保存による重負荷特性
の低下を抑制し、実用上問題のない筒形アルカリ電池を
提供することができた。As described above, in the present invention, by adding a lithium salt as a corrosion inhibitor for zinc to the electrolytic solution, corrosion of zinc is suppressed and generation of hydrogen gas from zinc is suppressed. The surface of the negative electrode current collector is plated with at least one metal selected from the group consisting of zinc, tin and lead to suppress generation of hydrogen gas from the contact portion between the negative electrode current collector and zinc. And the concentration of potassium hydroxide in the electrolytic solution is 35 to 45% by weight, particularly 37 to 4%.
2% by weight, and the concentration of zinc oxide is 3 to 7% by weight, especially 5
By setting the content to be at least wt%, it is possible to provide a cylindrical alkaline battery that suppresses deterioration of heavy load characteristics due to storage and has no practical problems.
【図１】本発明に係るアルカリ電池の一例を示す部分断
面図である。FIG. 1 is a partial cross-sectional view showing an example of an alkaline battery according to the present invention.
１ 正極合剤 ３ セパレータ ４ 負極剤 ５ 負極集電体 1 Positive Electrode Mixture 3 Separator 4 Negative Electrode 5 Negative Electrode Current Collector
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉原 正悦 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 (72)発明者 美和 優 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaetsu Sugihara 1-88, Torora, Ibaraki City, Osaka Prefecture Hitachi Maxel Co., Ltd. (72) Inventor Yu Miwa 1-88, Torora, Ibaraki City, Osaka Maxel Co., Ltd.
Claims (2)
筒形アルカリ電池において、亜鉛の腐食抑制剤としてリ
チウム塩を電解液に添加し、負極集電体の表面を亜鉛、
スズおよび鉛よりなる群から選ばれた少なくとも１種の
金属でメッキし、かつ電解液中の水酸化カリウムの濃度
が３５〜４５重量％で、酸化亜鉛の濃度が３〜７重量％
であることを特徴とする筒形アルカリ電池。1. In a cylindrical alkaline battery using anhydrous silver as a negative electrode active material, a lithium salt is added to an electrolytic solution as a corrosion inhibitor of zinc, and the surface of a negative electrode current collector is zinc.
The plating is performed with at least one metal selected from the group consisting of tin and lead, and the concentration of potassium hydroxide in the electrolytic solution is 35 to 45% by weight and the concentration of zinc oxide is 3 to 7% by weight.
A cylindrical alkaline battery characterized in that
加量が亜鉛に対して０．０５〜１０重量％である請求項
１記載の筒形アルカリ電池。2. The cylindrical alkaline battery according to claim 1, wherein the lithium salt is lithium hydroxide, and the addition amount thereof is 0.05 to 10% by weight with respect to zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3326574A JPH05135776A (en) | 1991-11-13 | 1991-11-13 | Cylindrical alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3326574A JPH05135776A (en) | 1991-11-13 | 1991-11-13 | Cylindrical alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05135776A true JPH05135776A (en) | 1993-06-01 |
Family
ID=18189336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3326574A Pending JPH05135776A (en) | 1991-11-13 | 1991-11-13 | Cylindrical alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05135776A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP2002093426A (en) * | 2000-09-12 | 2002-03-29 | Toshiba Battery Co Ltd | Battery |
| JP2002093413A (en) * | 2000-09-12 | 2002-03-29 | Toshiba Battery Co Ltd | Battery |
| JP2003536230A (en) * | 2000-06-19 | 2003-12-02 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Alkaline electrochemical battery |
| JP2004139909A (en) * | 2002-10-18 | 2004-05-13 | Toshiba Battery Co Ltd | Sealed nickel-zinc primary battery |
| WO2005112155A1 (en) * | 2004-05-13 | 2005-11-24 | Matsushita Electric Industrial Co., Ltd. | Alkaline battery |
| JP2006156158A (en) * | 2004-11-30 | 2006-06-15 | Sony Corp | Aa type alkaline battery |
| WO2006095683A1 (en) * | 2005-03-07 | 2006-09-14 | Fukui Byora Co., Ltd. | Negative electrode collector for dry cell |
| JP2007173220A (en) * | 2005-11-22 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Alkaline battery and method for producing the same |
| JP2008532256A (en) * | 2005-03-11 | 2008-08-14 | ザ ジレット カンパニー | battery |
| JP2010518585A (en) * | 2007-02-12 | 2010-05-27 | パワージェニックス システムズ， インコーポレーテッド | Zinc metal current collector |
| JP2017531295A (en) * | 2014-10-15 | 2017-10-19 | スペクトラム ブランズ インコーポレイテッド | Surfactant for zinc-air battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003536230A (en) * | 2000-06-19 | 2003-12-02 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Alkaline electrochemical battery |
| JP4503790B2 (en) * | 2000-06-21 | 2010-07-14 | 東芝電池株式会社 | Alkaline battery |
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP2002093426A (en) * | 2000-09-12 | 2002-03-29 | Toshiba Battery Co Ltd | Battery |
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| JP2004139909A (en) * | 2002-10-18 | 2004-05-13 | Toshiba Battery Co Ltd | Sealed nickel-zinc primary battery |
| WO2005112155A1 (en) * | 2004-05-13 | 2005-11-24 | Matsushita Electric Industrial Co., Ltd. | Alkaline battery |
| JP2005327541A (en) * | 2004-05-13 | 2005-11-24 | Matsushita Electric Ind Co Ltd | Alkaline battery |
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| JP2006156158A (en) * | 2004-11-30 | 2006-06-15 | Sony Corp | Aa type alkaline battery |
| JP4514588B2 (en) * | 2004-11-30 | 2010-07-28 | ソニー株式会社 | AA alkaline batteries |
| WO2006095683A1 (en) * | 2005-03-07 | 2006-09-14 | Fukui Byora Co., Ltd. | Negative electrode collector for dry cell |
| JP2008532256A (en) * | 2005-03-11 | 2008-08-14 | ザ ジレット カンパニー | battery |
| JP2007173220A (en) * | 2005-11-22 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Alkaline battery and method for producing the same |
| JP2010518585A (en) * | 2007-02-12 | 2010-05-27 | パワージェニックス システムズ， インコーポレーテッド | Zinc metal current collector |
| US8940430B2 (en) | 2007-02-12 | 2015-01-27 | Powergenix Systems, Inc. | Metallic zinc-based current collector |
| JP2017531295A (en) * | 2014-10-15 | 2017-10-19 | スペクトラム ブランズ インコーポレイテッド | Surfactant for zinc-air battery |
| US10320041B2 (en) * | 2014-10-15 | 2019-06-11 | Energizer Brands, Llc | Zinc-air battery surfactants |
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