JPH02276152A - Manganese dry battery - Google Patents

Manganese dry battery

Info

Publication number
JPH02276152A
JPH02276152A JP1097149A JP9714989A JPH02276152A JP H02276152 A JPH02276152 A JP H02276152A JP 1097149 A JP1097149 A JP 1097149A JP 9714989 A JP9714989 A JP 9714989A JP H02276152 A JPH02276152 A JP H02276152A
Authority
JP
Japan
Prior art keywords
added
dry battery
zinc
electrolyte
weight
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
Application number
JP1097149A
Other languages
Japanese (ja)
Inventor
Kenichi Shinoda
健一 篠田
Hirohiko Ota
太田　廣彦
Takashi Matsuo
隆 松尾
Nobuaki Watanabe
渡辺　信昭
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.)
FDK Corp
Original Assignee
FDK Corp
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 FDK Corp filed Critical FDK Corp
Priority to JP1097149A priority Critical patent/JPH02276152A/en
Publication of JPH02276152A publication Critical patent/JPH02276152A/en
Pending legal-status Critical Current

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cell Separators (AREA)
  • Primary Cells (AREA)

Abstract

PURPOSE:To retard the corrosion of a zinc can during storage to increase storage performance by using a paper material coated with a paste material to which an ester type polyethylene glycol family nonionic surface active agent is added as a separator. CONSTITUTION:In a manganese dry battery obtained by accommodating a positive mix 1 in a zinc can 3 through a separator 2, a paper material coated with a paste material to which an ester type polyethylene glycol family nonionic surface active agent in which the addition number of ethylene oxides is 8 or more is added is used as the separator 2. This surface active agent may be added to an electrolyte which is to be added to the positive mix instead of adding to the paste material. The preferable content of the surface active agent is 0.25-0.5wt.% based on the weight of the paste material constituents when it is added to the paste material and 0.005-0.01wt.% based on the weight of electrolyte constituents when it is added to the electrolyte.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 この発明は、マンガン乾電池に関するものである。[Detailed description of the invention] <Industrial application field> This invention relates to a manganese dry battery.

〈従来の技術〉 マンガン乾電池は、二酸化マンガンとアセチレンブラッ
クを主成分とする混合粉体に塩化亜鉛溶液や塩化アンモ
ニウム溶液などからなる電解液を加え、またこれらを混
合し成形して作った正極合剤を、紙材に糊材を塗布した
セパレータを介゛して、負極亜鉛缶内に収納する（Ｒ成
を採っている。<Conventional technology> Manganese dry batteries are made by adding an electrolyte consisting of a zinc chloride solution or an ammonium chloride solution to a powder mixture whose main components are manganese dioxide and acetylene black, and then mixing and molding the mixture. The agent is stored in a negative electrode zinc can via a separator made of paper coated with adhesive (R configuration is adopted).

ところで、このマンガン乾電池では、正極合剤中の二酸
化マンガンとして、コストが比較的に安価な天然二酸化
マンガンが電解二酸化マンガンなどと混合して使用され
ているが、例えばこの天然二酸化マンガン中には、鉄や
銅などの不純物が含まれることから、これらの不純物と
亜鉛及び乾電池内の電解液により局部電池が形成され、
このためストック中において亜鉛缶が腐蝕を受けて消費
（自己放電）するという欠点がある。By the way, in this manganese dry battery, relatively inexpensive natural manganese dioxide is used as the manganese dioxide in the positive electrode mixture, mixed with electrolytic manganese dioxide, etc., but for example, in this natural manganese dioxide, Because it contains impurities such as iron and copper, a local battery is formed by these impurities, zinc, and the electrolyte in the dry battery.
For this reason, there is a disadvantage that the zinc cans are corroded and consumed (self-discharged) while in stock.

そして、この腐蝕が進行すると亜鉛缶の孔食が生じるし
、またその際発生する水素ガスによって乾７１／ｌｌ！
の内圧が上昇するので漏液の発生率が高まり、更にほこ
の亜鉛缶消費により乾電池の放電性能が低下するなどの
不都合がある。As this corrosion progresses, pitting corrosion occurs in the zinc can, and the hydrogen gas generated at this time causes dry 71/ll!
Since the internal pressure of the battery increases, the rate of leakage increases, and furthermore, the discharging performance of the dry battery decreases due to consumption of the zinc can.

この現象は高温時において顕著に起こり、従って高温貯
蔵後における乾電池の性能低下が特に大きい。This phenomenon occurs conspicuously at high temperatures, and therefore the performance of the dry cell battery deteriorates particularly significantly after high temperature storage.

このような性能の低下を抑制して乾電池の貯蔵性能の向
上を図るための手段としては、通常、水銀を用いたアマ
ルガム化処理が行なわれている。即ち、この処理では、
例えばセパレータ紙材に塗布する糊材に可溶性の水銀（
ＨｇＣｇ２）を混入・添加することで、亜鉛缶内面をア
マルガム化してその水素過電圧を高め、亜鉛缶の腐蝕（
自己放電）を抑制するようにしている。Amalgamation treatment using mercury is usually performed as a means for suppressing such performance deterioration and improving the storage performance of dry batteries. That is, in this process,
For example, soluble mercury (
By mixing and adding HgCg2), the inner surface of the zinc can is amalgamated, its hydrogen overvoltage is increased, and corrosion of the zinc can (
self-discharge).

〈発明が解決しようとする課題〉 しかしながら、上記のアマルガム化処理の場合、乾電池
に微量といえども人体に有害な水銀が含まれる。このた
め、水銀が社会問題として取上げられている現在、マン
ガン乾電池においても無水銀化が強く望まれている。<Problems to be Solved by the Invention> However, in the case of the above-mentioned amalgamation treatment, the dry battery contains mercury, which is harmful to the human body, even if it is in a small amount. For this reason, now that mercury is being taken up as a social issue, there is a strong desire for mercury-free manganese dry batteries as well.

この発明は、亜鉛防蝕性能が優れた特定のインヒビター
を用いることで、水銀による亜鉛缶内面のアマルガム化
処理なしに乾電池の上記貯蔵性能の低下を有効に抑制す
ることのできるマンガン乾電池を提供することを目的と
する。The present invention provides a manganese dry battery that can effectively suppress the deterioration of storage performance of the dry battery without amalgamating the inner surface of the zinc can with mercury by using a specific inhibitor with excellent zinc corrosion prevention performance. With the goal.

く課題を解決するための手段〉 この発明のマンガン乾電池は、亜鉛缶内にセパレータを
介して正極合剤を収納してなるマンガン乾電池において
、前記セパレータとして、エチレンオキサイドの付加モ
ル数が８以上でエステル型のポリエチレングリコール系
非イオン界面活性剤を添加した糊材を紙材に塗布したも
のを用いたことを要旨とする。Means for Solving the Problems> The manganese dry battery of the present invention is a manganese dry battery in which a positive electrode mixture is housed in a zinc can with a separator interposed therebetween, in which the number of moles of ethylene oxide added as the separator is 8 or more. The gist is that a paper material coated with a glue material containing an ester type polyethylene glycol nonionic surfactant was used.

上記の界面活性剤としては、例えば次式で示されるもの
が挙げられる。これは、例えば、東邦化学工業■の「ベ
グノール」として入手することができる。Examples of the above-mentioned surfactants include those represented by the following formula. This can be obtained, for example, as "Begnol" from Toho Chemical Industry (■).

Ｒ−Ｃ−０−（ＥＯ）　　　　Ｈ 上式において、ＥＯはエチレンオキサイド。R-C-0-(EO)　　H In the above formula, EO is ethylene oxide.

ｍは８以上の整数をそれぞれ表す。m represents an integer of 8 or more.

一方、Ｒはアルキル基を表し、具体的には、例えばＣＨ
−（Ｃ２Ｈ４）。（ｎは好ましくは５〜８の整数）を指
す。On the other hand, R represents an alkyl group, specifically, for example, CH
-(C2H4). (n is preferably an integer of 5 to 8).

また、上記のように糊材に添加することに代え、この界
面活性剤を、正極合剤に混合する電解液中に、添加する
構成としても良い。Further, instead of adding the surfactant to the glue material as described above, the surfactant may be added to the electrolytic solution mixed with the positive electrode mixture.

そして、この界面活性剤の好ましい添加量は、糊材に添
加する場合は糊材の組成物に対して０２５〜０．５重量
％、また電解液に添加する場合には電解液の組成物に対
して０．ＱＯ５〜０．ロー重量％とすればよい。この範
囲より少ないと亜鉛の防蝕性が不十分となり、またこの
範囲を越えて必要以上にいれた場合、防蝕性に変化はな
いものの、放電性能が大きく低下する虞がある。The preferred amount of this surfactant to be added is 0.25 to 0.5% by weight based on the composition of the glue when added to the glue, and 0.25 to 0.5% by weight based on the composition of the glue when added to the electrolyte. Against 0. QO5~0. Low weight % may be used. If the amount is less than this range, the corrosion resistance of zinc will be insufficient, and if the amount exceeds this range and is added more than necessary, there is a risk that the discharge performance will be greatly reduced, although there will be no change in the corrosion resistance.

本発明において、正極合剤に用いる二酸化マンガンとし
ては、電解二酸化マンガン、天然二酸化マンガンあるい
は化学二酸化マンガンなどを用いることができる。また
、正極合剤に混合する導電材には、コークカーボン粉、
黒鉛、アセチレンブラックなどが使用され、特に電解液
保持力の高いアセチレンブラックが好ましい。In the present invention, as the manganese dioxide used in the positive electrode mixture, electrolytic manganese dioxide, natural manganese dioxide, chemical manganese dioxide, or the like can be used. In addition, the conductive material mixed into the positive electrode mixture includes coke carbon powder,
Graphite, acetylene black, etc. are used, and acetylene black, which has a high electrolyte retention ability, is particularly preferred.

また、正極合剤や糊材に用いる電解液には、Ｚ　ｎＣＩ
Ｉ　　　Ｎ　Ｈ４Ｃｉ！の他、耐寒電池用としてはＭｇ
Ｃ２ＬｉＣΩ、　Ｃａ　Ｃ，９２などを２′ 用いれば良い。In addition, Z nCI is used in the electrolyte used for the positive electrode mixture and glue material.
I N H4Ci! In addition, Mg is used for cold-resistant batteries.
C2LiCΩ, CaC,92, etc. may be used as 2'.

一方、セパレータに用いる糊材中の澱粉としては、トウ
モロコシ澱粉、小麦澱粉、ジャガイモ澱粉などを用いる
ことができるが、耐漏液特性を重視する場合には、トウ
モロコシ澱粉をホルマール化処理した架橋澱粉が使用さ
れる。On the other hand, corn starch, wheat starch, potato starch, etc. can be used as the starch in the glue material used for the separator, but if leakage resistance is important, cross-linked starch obtained by formalizing corn starch is used. be done.

く作用〉 上記の界面活性剤を糊材や電解液に添加することで、亜
鉛缶内面にこの界面活性剤が付着する。つまり、亜鉛缶
側にはこの界面活性剤の非イオン系親水基が強力に吸着
し、一方界面活性剤の疎水基Ｒ−が電解液を遮蔽するよ
うに機能する。Effect> By adding the above surfactant to the glue material or electrolyte, the surfactant adheres to the inner surface of the zinc can. That is, the nonionic hydrophilic group of this surfactant strongly adsorbs to the zinc can side, while the hydrophobic group R- of the surfactant functions to shield the electrolyte.

そして、上記のようにエチレンオキサイドの付加モル数
を８以上とすることで、長期にわたり安定した防蝕効果
が得られる。As mentioned above, by setting the number of moles of ethylene oxide added to 8 or more, a stable anticorrosion effect can be obtained over a long period of time.

この結果、ストック中の亜鉛缶の腐蝕が抑制され、貯蔵
性能の低下が有効に防止される。As a result, corrosion of the zinc cans in stock is suppressed, and deterioration in storage performance is effectively prevented.

〈実施例〉 実施例１ 天然二酸化マンガン３０重量部と電解二酸化マンガン５
０重量部及びアセチレンブラック２０重量部との混合物
を主成分とする混合粉体に、水ｔｏｏ重量部と塩化亜鉛
（Ｚ　ｎ　Ｃｆｌ　２）　３５重量部並びに塩化アンモ
ニウム（ＮＨ４１？）５重量部からなる電解液を加え、
これらを混合後に円筒状に成形して、正極合剤（合剤型
ｆｆｉ５５ｇ）を作った。<Example> Example 1 30 parts by weight of natural manganese dioxide and 5 parts by weight of electrolytic manganese dioxide
0 parts by weight of acetylene black and 20 parts by weight of acetylene black, too many parts by weight of water, 35 parts by weight of zinc chloride (ZnCfl2) and 5 parts by weight of ammonium chloride (NH41?). Add electrolyte,
After mixing these, they were molded into a cylindrical shape to produce a positive electrode mixture (mixture type ffi 55 g).

また、糊材として、トウモロコシ澱粉２０重量部　５０
％塩化亜鉛水溶液５重量部、２５％塩化アンモニウム水
溶液５重量部、水７０重量部の組成のものを混練し、ま
た下式に示すエステル型のポリエチレングリコール系非
イオン界面活性剤（エチレンオキサイドの付加モル数ｍ
がそれぞれ５．８．１０．１５　）を、この組成物に対
してそれぞれ０．２５ｆｆｔｍ％添加したものを作った
。In addition, as a glue material, 20 parts by weight of corn starch 50
% zinc chloride aqueous solution, 5 parts by weight of 25% ammonium chloride aqueous solution, and 70 parts by weight of water were kneaded, and an ester type polyethylene glycol nonionic surfactant (addition of ethylene oxide) shown in the following formula was kneaded. Number of moles m
5.8, 10.15), respectively, were added to this composition in an amount of 0.25 fftm%.

そして、添附図面の通り、正極合剤１を、上記糊材を塗
布した紙セパレータ２を介して亜鉛缶３内に収納して、
Ｒ２０の本発明に係わるマンガン乾電池を作製した（本
発明乾電池１）。図において４〜１０は、それぞれ、炭
素棒、封ロガスケット、正極端子板、負極端子板、熱収
縮性樹脂チューブ、外装缶、底紙を指す。Then, as shown in the attached drawings, the positive electrode mixture 1 is stored in a zinc can 3 via a paper separator 2 coated with the above-mentioned adhesive.
A manganese dry battery of R20 according to the present invention was produced (dry battery of the present invention 1). In the figure, 4 to 10 respectively refer to a carbon rod, a sealing gasket, a positive terminal plate, a negative terminal plate, a heat-shrinkable resin tube, an outer can, and a bottom paper.

また、糊材における上記界面活性剤の添加量を０．５重
量％とした他は同様にして、Ｒ２０の本発明に係わるマ
ンガン乾電池を作製した（本発明乾電池２）。Further, an R20 manganese dry battery according to the present invention was produced in the same manner except that the amount of the surfactant added to the adhesive was 0.5% by weight (present invention dry battery 2).

更に、この界面活性剤に代えて、塩化水銀を糊材に対し
０゜２５％添加した他は同様にして、Ｒ２０の比較用の
マンガン乾電池（比較乾電池１）を、また界面活性剤や
塩化水銀などの添加剤を使用しない他は同様にして、Ｒ
２０の比較用のマンガン乾電池（比較乾電池２）をそれ
ぞれ作った。Furthermore, instead of this surfactant, mercury chloride was added at 0°25% to the glue material, but a comparative R20 manganese dry battery (comparative dry battery 1) was prepared in the same manner, and a surfactant and mercury chloride were added. Similarly, R
Twenty comparative manganese dry batteries (comparative dry battery 2) were each made.

これらの乾電池について、製造後に環境温度４５℃にて
３ケ月保存した後、それらの開路電圧（Ｖ）、並びに亜
鉛缶の減量（ｍｇ　）をそれぞれ７１Ｆ＋定した。本発
明乾電池１．２の結果は第１表に、また比較乾電池１．
２の結果は第２表にそれぞれ示した。These dry batteries were stored for 3 months at an environmental temperature of 45° C. after manufacture, and then their open circuit voltage (V) and zinc can weight loss (mg 2 ) were determined to be 71 F+, respectively. The results for the dry battery 1.2 of the present invention are shown in Table 1, and the results for the dry battery 1.2 for comparison are shown in Table 1.
The results of 2 are shown in Table 2.

第１表 第２表 実施例２ 一方、紙セパレータに塗布する糊材にトウモロコシ澱粉
２０重量部、５０％塩化亜鉛水溶液５重量部、２５％塩
化アンモニウム水溶液５重量部、水７０重量部の組成の
ものを用いる一方、正極合剤に混合する電解液として、
水１００重量部と塩化亜鉛３５重量部並びに塩化アンモ
ニウム５重量部の組成のものに、上式に示した界面活性
剤（エチレンオキサイドの付加モル数ｍがそれぞれ５．
　８．１０．１５　）を、この組成物に対しそれぞれ０
．００５重量％添加した電解液を用いた他は上記と同様
にして、Ｒ２０のマンガン乾電池（本発明乾電池３）を
作った。Table 1 Table 2 Example 2 On the other hand, the glue material to be applied to the paper separator had a composition of 20 parts by weight of corn starch, 5 parts by weight of a 50% aqueous zinc chloride solution, 5 parts by weight of a 25% aqueous ammonium chloride solution, and 70 parts by weight of water. On the other hand, as an electrolyte to be mixed with the positive electrode mixture,
To a composition of 100 parts by weight of water, 35 parts by weight of zinc chloride, and 5 parts by weight of ammonium chloride, the surfactant shown in the above formula (the number of moles of ethylene oxide added is 5.
8.10.15) respectively 0 for this composition.
．． An R20 manganese dry battery (invention dry battery 3) was produced in the same manner as above except that an electrolyte containing 0.005% by weight was used.

また、電解液中への上記界面活性剤の添加量を０．０１
重量％とした他は同様にして、Ｒ２０のマンガン乾電池
（本発明乾電池４）を作製した。In addition, the amount of the surfactant added to the electrolyte was 0.01
An R20 manganese dry battery (dry battery of the present invention 4) was produced in the same manner except that the weight % was changed.

これらの乾電池を、実施例１と同じく環境温度４５℃で
３ケ月間保存後における開路電圧（Ｖ）並びに亜鉛缶減
量（ａｇ　）をそれぞれ測定した。The open circuit voltage (V) and zinc can weight loss (ag) of these dry batteries after being stored for 3 months at an environmental temperature of 45° C. as in Example 1 were measured.

この結果を第３表に示した。The results are shown in Table 3.

第３表 〈発明の効果〉 以上の通り、この発明によれば、水銀によるアマルガム
化処理をすることなしに、ストック時における亜鉛の腐
蝕を実用上十分な程度に抑制することができ、従って無
水化でも貯蔵性能の優れたマンガン乾電池を提供するこ
とができる。Table 3 <Effects of the Invention> As described above, according to the present invention, corrosion of zinc during stocking can be suppressed to a practically sufficient degree without amalgamation treatment with mercury, and therefore anhydrous It is possible to provide a manganese dry battery with excellent storage performance.

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

添付図面は、実施例で用いた乾電池の断面図である。 １・・・正極合剤、２・・・紙セパレータ、３・・・亜
鉛缶。The attached drawing is a cross-sectional view of the dry battery used in the example. 1... Positive electrode mixture, 2... Paper separator, 3... Zinc can.

Claims (1)

【特許請求の範囲】 １、亜鉛缶内にセパレータを介して正極合剤を収納して
なるマンガン乾電池において、前記セパレータとして、
エチレンオキサイドの付加モル数が８以上でエステル型
のポリエチレングリコール系非イオン界面活性剤を添加
した糊材を紙材に塗布したものを用いたことを特徴とす
るマンガン乾電池。 ２、二酸化マンガンを主成分とする活物質を電解液とと
もに混合してなる正極合剤を、セパレータを介して亜鉛
缶内に収納して構成されるマンガン乾電池において、前
記電解液に請求項１記載の界面活性剤を添加したことを
特徴とするマンガン乾電池。[Claims] 1. In a manganese dry battery in which a positive electrode mixture is housed in a zinc can via a separator, as the separator:
A manganese dry battery characterized by using a paper material coated with a glue material containing an ester type polyethylene glycol nonionic surfactant with an added mole number of ethylene oxide of 8 or more. 2. A manganese dry battery configured by storing a positive electrode mixture formed by mixing an active material mainly composed of manganese dioxide with an electrolyte in a zinc can with a separator interposed therebetween, in which the electrolyte is added to the electrolyte according to claim 1. A manganese dry battery characterized by adding a surfactant.
JP1097149A 1989-04-17 1989-04-17 Manganese dry battery Pending JPH02276152A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1097149A JPH02276152A (en) 1989-04-17 1989-04-17 Manganese dry battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1097149A JPH02276152A (en) 1989-04-17 1989-04-17 Manganese dry battery

Publications (1)

Publication Number Publication Date
JPH02276152A true JPH02276152A (en) 1990-11-13

Family

ID=14184515

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1097149A Pending JPH02276152A (en) 1989-04-17 1989-04-17 Manganese dry battery

Country Status (1)

Country Link
JP (1) JPH02276152A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002043169A3 (en) * 2000-11-22 2002-08-29 Electric Fuel Ltd Metal-alkaline battery cells with reduced corrosion rates
WO2019181050A1 (en) * 2018-03-23 2019-09-26 パナソニックＩｐマネジメント株式会社 Alkaline dry battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002043169A3 (en) * 2000-11-22 2002-08-29 Electric Fuel Ltd Metal-alkaline battery cells with reduced corrosion rates
WO2019181050A1 (en) * 2018-03-23 2019-09-26 パナソニックＩｐマネジメント株式会社 Alkaline dry battery
CN111587504A (en) * 2018-03-23 2020-08-25 松下知识产权经营株式会社 Alkaline dry cell
US11581549B2 (en) 2018-03-23 2023-02-14 Panasonic Intellectual Property Management Co., Ltd. Alkaline dry batteries
CN111587504B (en) * 2018-03-23 2023-05-02 松下知识产权经营株式会社 Alkaline dry cell

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