JPH0619993B2 - Zinc alkaline battery - Google Patents
Zinc alkaline batteryInfo
- Publication number
- JPH0619993B2 JPH0619993B2 JP60131638A JP13163885A JPH0619993B2 JP H0619993 B2 JPH0619993 B2 JP H0619993B2 JP 60131638 A JP60131638 A JP 60131638A JP 13163885 A JP13163885 A JP 13163885A JP H0619993 B2 JPH0619993 B2 JP H0619993B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- weight
- cobalt
- nickel
- 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.)
- Expired - Lifetime
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)
Description
【発明の詳細な説明】 (発明の分野) 本発明は亜鉛アルカリ電池に関し、詳しくはインジウ
ム、タリウムより選ばれる、 1種以上とコバルトとニッ
ケルを特定範囲で含有した亜鉛合金をそのまま、もしく
は汞化して電池用負極活物質として用いた亜鉛アルカリ
電池に関する。Description: FIELD OF THE INVENTION The present invention relates to a zinc alkaline battery, and more specifically, to a zinc alloy containing at least one selected from indium and thallium and cobalt and nickel in a specific range, or selectively converted into a zinc alloy. The present invention relates to a zinc alkaline battery used as a negative electrode active material for a battery.
(発明の背景) 亜鉛を負極活物質として用いたアルカリ電池等において
は、水酸化カリウム水溶液等の強アルカリ性電解液を用
いるため、電池を密閉しなければならない。この電池の
密閉は電池の小型化を図る際には特に重要であるが、同
時に電池保存中の亜鉛の腐食により発生する水素ガスを
閉じ込めることになる。従って長期保存中に電池内部の
ガス圧が高まり、密閉が完全なほど爆発等の危険が伴な
う。(Background of the Invention) In an alkaline battery or the like using zinc as a negative electrode active material, a strong alkaline electrolyte such as an aqueous potassium hydroxide solution is used, and therefore the battery must be sealed. This sealing of the battery is particularly important for miniaturization of the battery, but at the same time, it confine hydrogen gas generated by corrosion of zinc during battery storage. Therefore, the gas pressure inside the battery increases during long-term storage, and there is a danger of explosion and the like if the sealing is perfect.
その対策として、負極活物質である亜鉛の腐食を防止し
て、電池内部の水素ガス発生を少なくすることが研究さ
れ、水銀の水素過電圧を利用した汞化亜鉛を負極活物質
として用いることが専ら行なわれている。このため、今
日市販されているアルカリ電池の負極活物質は 5〜10重
量%程度の多量の水銀を含有しており、社会的ニーズと
して、より低水銀のもの、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。As a countermeasure against this, research has been conducted to prevent corrosion of zinc, which is the negative electrode active material, to reduce the generation of hydrogen gas inside the battery, and to use zinc hydride, which utilizes the hydrogen overvoltage of mercury, as the negative electrode active material. Has been done. For this reason, the negative electrode active material for alkaline batteries currently on the market contains a large amount of mercury of about 5 to 10% by weight. It has become strongly expected.
そこで、電池内の水銀含有量を低減させるべく、亜鉛に
各種金属を添加した亜鉛合金粉末に関する提案が種々な
されている。例えば、亜鉛に鉛を添加した亜鉛合金粉
末、あるいは本発明者等による亜鉛に鉛とインジウムを
添加した亜鉛合金粉末(特開昭58-181266号公報)等が
ある。しかし、これらの亜鉛合金粉末はある程度のガス
発生抑制効果を奏するが、まだ十分とは言えない。Therefore, various proposals have been made regarding a zinc alloy powder in which various metals are added to zinc in order to reduce the mercury content in the battery. For example, there is a zinc alloy powder in which lead is added to zinc, or a zinc alloy powder in which lead and indium are added to zinc by the present inventors (JP-A-58-181266). However, although these zinc alloy powders have some gas generation suppressing effect, they are not yet sufficient.
このように、負極活物質である亜鉛合金粉末を低汞化と
しつつ、水素ガス発生量を低減し、しかも電池性能であ
る放電性能を高い水準に維持する電池は未だ得られてい
ない。As described above, a battery that reduces the amount of hydrogen gas generated while keeping the zinc alloy powder, which is the negative electrode active material, at a low level and maintains the discharge performance, which is the battery performance, at a high level has not yet been obtained.
(発明の目的) 本発明はかかる現状に鑑み、水銀の含有率を著しく減少
させつつ、水素ガス発生を抑制し、しかも放電性能を高
い水準に維持する負極活物質を用い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 present circumstances, the present invention provides a zinc-alkaline battery using a negative electrode active material that significantly reduces the content of mercury, suppresses hydrogen gas generation, and maintains discharge performance at a high level. The purpose is to do.
(発明の経緯) 本発明者らはこの目的に沿って鋭意研究の結果、亜鉛か
らなる負極活物質において、インジウム、タリウムより
選ばれる 1種以上とコバルトとニッケルを特定範囲の量
添加することにより、これら添加元素の相乗的な効果に
よって、従来の低汞化した亜鉛合金粉末よりも更に水素
ガス発生量を低下させ、しかも放電性能に優れた亜鉛ア
ルカリ電池が得られることを見出し本発明に到達した。(History of the invention) As a result of intensive research aimed at achieving this object, the present inventors have found that by adding at least one selected from indium and thallium, and cobalt and nickel in a specific range to a negative electrode active material made of zinc. The present inventors have found that the synergistic effect of these additive elements further reduces the hydrogen gas generation amount as compared with the conventional low-alloyed zinc alloy powder, and that a zinc alkaline battery having excellent discharge performance can be obtained and has reached the present invention. did.
(発明の構成) すなわち本発明は、インジウム、タリウムより選ばれる
1種以上を合計0.01〜0.5重量%、コバルトを
0.01〜0.5重量%、ニッケルを0.01〜0.5
重量%含有する亜鉛合金を負極活物質として用いたこと
を特徴とする亜鉛アルカリ電池にある。(Structure of Invention) That is, the present invention is selected from indium and thallium.
0.01-0.5% by weight, 0.01-0.5% by weight cobalt, 0.01-0.5% nickel
A zinc alkaline battery is characterized by using a zinc alloy containing wt% as a negative electrode active material.
本発明において、インジウム、タリウムより選ばれる 1
種以上とコバルトとニッケルを特定量添加した亜鉛合金
は、そのまま負極活物質として用いるか、亜鉛合金を汞
化し後に負極活物質として用いる。汞化する場合の水銀
含有率は、従来の負極活物質の水銀含有率よりも少ない
量、すなわち5.0重量%未満であるが、より汞化率を
低くし、低公害性を考慮すると3.0重量%以下であ
る。また、1.0重量%前後またはそれ以下の少量であ
ってもガス発生を抑制することが可能である。特に、排
気機構を備えた空気電池や水素吸収機構を備えた亜鉛ア
ルカリ電池等においては、水素ガスの発生許容量は比較
的大きいので、このような電池に本発明を適用する場合
は、1.0重量%以下の低汞化率または無汞化の亜鉛合
金が負極活物質として好ましく用いられる。In the present invention, selected from indium and thallium 1
The zinc alloy containing at least one species and a specific amount of cobalt and nickel may be used as the negative electrode active material as it is, or may be used as the negative electrode active material after grading the zinc alloy. The mercury content in the case of conversion is less than the mercury content of the conventional negative electrode active material, that is, less than 5.0% by weight, but if the conversion rate is lowered and low pollution is considered, it is 3 It is not more than 0.0% by weight. Further, it is possible to suppress gas generation even with a small amount of around 1.0% by weight or less. In particular, in an air battery provided with an exhaust mechanism, a zinc alkaline battery provided with a hydrogen absorption mechanism, and the like, the permissible hydrogen gas generation amount is relatively large. Therefore, when the present invention is applied to such a battery, 1. A zinc alloy having a low weight reduction rate of 0% by weight or less or a weight loss-free zinc alloy is preferably used as the negative electrode active material.
この負極活物質に用いられる亜鉛合金のインジウム、タ
リウムより選ばれる 1種以上の含有率は0.01〜0.
5重量%、コバルトの含有率は0.01〜0.5重量
%、ニッケルの含有率は0.01〜0.5重量%と少量
で添加効果が発揮される。インジウム、タリウムより選
ばれる 1種以上とコバルトとニッケルの含有率がそれぞ
れ下限未満では本発明の効果が得られず、上限を越える
と、不純物を含有した亜鉛のように、自己放電が進み、
ガス発生抑制および放電性能にとって良好な結果が得ら
れない。The content of one or more selected from indium and thallium in the zinc alloy used for this negative electrode active material is 0.01 to 0.
5% by weight, the content of cobalt is 0.01 to 0.5% by weight, and the content of nickel is 0.01 to 0.5% by weight. If the content of one or more selected from indium and thallium and the content of cobalt and nickel are less than the respective lower limits, the effect of the present invention cannot be obtained, and if it exceeds the upper limit, self-discharge proceeds like zinc containing impurities.
Good results cannot be obtained for suppressing gas generation and discharging performance.
これら各添加元素の作用効果は充分に解明されていない
が、推定するに、亜鉛合金中に含まれているインジウ
ム、タリウムは水素過電圧を高める作用を有し、コバル
トおよびニッケルについてはそれ自体耐食性のある金属
であることは知られているが、亜鉛と溶体化した場合に
も局部腐食反応の抑制に役立つと考えられる。また、亜
鉛合金を表面から汞化した場合、水銀と親和性の小さい
コバルトおよびニッケルが亜鉛合金内部への水銀の拡散
を抑制し、亜鉛合金表面の水銀濃度を高く維持すること
により耐食性の向上に役立つと考えられる。Although the action and effect of each of these additional elements have not been sufficiently clarified, it is presumed that indium and thallium contained in the zinc alloy have an action of increasing hydrogen overvoltage, and cobalt and nickel have corrosion resistance themselves. Although it is known to be a metal, it is thought to be useful for suppressing the local corrosion reaction even when it is solutionized with zinc. In addition, when the zinc alloy is modified from the surface, cobalt and nickel, which have a low affinity for mercury, suppress the diffusion of mercury into the zinc alloy and maintain a high mercury concentration on the surface of the zinc alloy to improve corrosion resistance. Thought to be useful.
本発明は、これら各作用の相乗効果により、放電特性を
劣化させることなく、耐食性のよい亜鉛合金が得られた
ものである。The present invention provides a zinc alloy having good corrosion resistance without deteriorating discharge characteristics due to the synergistic effect of each of these actions.
このように本発明の亜鉛アルカリ電池は、電解液に苛性
カリ、苛性ソーダ等を主成分とするアルカリ水溶液を用
い、負極活物質に上記した亜鉛合金または汞化した亜鉛
合金、正極活物質に二酸化マンガン、酸化銀、酸素等を
用いることにより得られる。Thus, the zinc-alkaline battery of the present invention uses caustic potash as an electrolytic solution, an aqueous alkaline solution containing caustic soda as a main component, the above-mentioned zinc alloy or delayed zinc alloy as the negative electrode active material, and manganese dioxide as the positive electrode active material. It can be obtained by using silver oxide, oxygen or the like.
(実施例の説明) 以下、実施例および比較例に基づいて本発明を具体的に
説明する。(Explanation of Examples) Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.
実施例1〜8および比較例1〜10 純度99.997%以上の亜鉛地金を約500℃で溶融し、これ
に第1表に示すごとくインジウム、コバルト、ニッケル
の含有率がそれぞれ0.05重量%となるように添加し
て亜鉛合金を作成し、これを高圧アルゴンガス(噴出圧
5kg/cm2)を使って粉体化した。津に水酸化カリウム1
0%のアルカリ性溶液中にて上記粉末に1.0重量%に
なるように水銀を添加して、汞化処理を行ない亜鉛合金
粉末(実施例1)を得た。Examples 1 to 8 and Comparative Examples 1 to 10 Zinc ingots having a purity of 99.997% or more are melted at about 500 ° C., and the indium, cobalt, and nickel contents are each 0.05 wt% as shown in Table 1. To make a zinc alloy, and add this to high pressure argon gas (jet pressure
It was pulverized using 5 kg / cm 2 ). Potassium hydroxide on Tsu 1
Mercury was added to the above powder in a 0% alkaline solution so as to be 1.0% by weight, and a grading treatment was performed to obtain a zinc alloy powder (Example 1).
また、第1表に示すごとく、下記の組成でそれぞれ、 1):タリウム0.05重量%、コバルト0.05重量
%、ニッケル0.05重量%(実施例2)、 2):インジウム0.01重量%、コバルト0.01重
量%、ニッケル0.01重量%(実施例3) 3):タリウム0.01重量%、コバルト0.01重量
%、ニッケル0.01重量%(実施例4)、 4):インジウム0.5重量%、コバルト0.5重量
%、ニッケル0.5重量%(実施例5)、 5):タリウム0.5重量%、コバルト0.5重量%、
ニッケル0.5重量%(実施例6)、 6):インジウム0.05重量%、タリウム0.05重
量%、コバルト0.05重量%、ニッケル0.05重量
%(実施例7)、 7):インジウム0.2重量%、タリウム0.3重量
%、コバルト0.5重量%、ニッケル0.5重量%(実
施例8)、 8):インジウム0.05重量%(比較例1)、 9):タリウム0.05重量%(比較例2)、 10):インジウム0.05重量%、コバルト0.05重
量%(比較例3)、 11):インジウム0.05重量%、ニッケル0.05重
量%(比較例4)、 12):インジウム1.0重量%、コバルト0.05重量
%、ニッケル0.05重量%(比較例5)、 13):インジウム0.005重量%、コバルト0.05
重量%、ニッケル0.05重量%(比較例6) 14):インジウム0.05重量%、コバルト1.0重量
%、ニッケル0.05重量%(比較例7)、 15):インジウム0.05重量%、コバルト0.005
重量%、ニッケル0.05重量%(比較例8) 16):インジウム0.05重量%、コバルト0.05重
量%、ニッケル1.0重量%(比較例9)、 17):インジウム0.05重量%、コバルト0.05重
量%、ニッケル0.005重量%(比較例10) からなる亜鉛合金をそれぞれ作成し、これを前記と同様
な方法で粉体化し、汞化処理を行なって水銀含有率が
1.0重量%の亜鉛合金粉末(実施例2〜8および比較
例1〜10)を得た。In addition, as shown in Table 1, 1): 0.05% by weight thallium, 0.05% by weight cobalt, 0.05% by weight nickel (Example 2), 2): indium 0. 01 wt%, cobalt 0.01 wt%, nickel 0.01 wt% (Example 3) 3): thallium 0.01 wt%, cobalt 0.01 wt%, nickel 0.01 wt% (Example 4) 4): indium 0.5% by weight, cobalt 0.5% by weight, nickel 0.5% by weight (Example 5), 5): thallium 0.5% by weight, cobalt 0.5% by weight,
Nickel 0.5 wt% (Example 6), 6): Indium 0.05 wt%, thallium 0.05 wt%, cobalt 0.05 wt%, nickel 0.05 wt% (Example 7), 7) : Indium 0.2% by weight, thallium 0.3% by weight, cobalt 0.5% by weight, nickel 0.5% by weight (Example 8), 8): indium 0.05% by weight (Comparative Example 1), 9 ): Thallium 0.05 wt% (Comparative Example 2), 10): Indium 0.05 wt%, Cobalt 0.05 wt% (Comparative Example 3), 11): Indium 0.05 wt%, Nickel 0.05 Wt% (Comparative Example 4), 12): 1.0 wt% indium, 0.05 wt% cobalt, 0.05 wt% nickel (Comparative Example 5), 13): 0.005 wt% indium, cobalt 0.1. 05
Wt%, nickel 0.05 wt% (Comparative Example 6) 14): indium 0.05 wt%, cobalt 1.0 wt%, nickel 0.05 wt% (Comparative Example 7), 15): indium 0.05 Wt%, cobalt 0.005
%, Nickel 0.05% by weight (Comparative Example 8) 16): indium 0.05% by weight, cobalt 0.05% by weight, nickel 1.0% by weight (Comparative Example 9), 17): indium 0.05 % Zinc, 0.05 wt.% Cobalt, and 0.005 wt.% Nickel (Comparative Example 10). Zinc alloys were prepared, respectively, which were pulverized by the same method as described above and subjected to a grading treatment to contain mercury. A zinc alloy powder (Examples 2-8 and Comparative Examples 1-10) having a rate of 1.0% by weight was obtained.
このようにして得られた亜鉛合金粉末を使って水素ガス
発生試験を行ない、その結果を第1表に示す。なお、ガ
ス発生試験は、電解液として濃度40重量%の水酸化カリ
ウム水溶液に酸化亜鉛を飽和させたものを 5ml用い、亜
鉛合金粉末を10gを用いて45℃で50日間のガス発生量
(ml/g)を測定した。A hydrogen gas generation test was performed using the zinc alloy powder thus obtained, and the results are shown in Table 1. In the gas generation test, 5 ml of 40 wt% potassium hydroxide aqueous solution saturated with zinc oxide was used as electrolyte, and 10 g of zinc alloy powder was used at 45 ° C for 50 days to generate gas (ml / G) was measured.
また、これらの亜鉛合金粉末を負極活物質として第1図
に示すアルカリマンガン電池を用いて電池性能を評価し
た。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、亜鉛合金粉末をカルボキシメチル
セルロースでゲル化した負極4、負極集電体5、ゴムパ
ッキン6、押さえ板7で構成されている。このアルカリ
マンガン電池を用いて放電負極 4Ω、20℃の放電条件に
より終止電圧0.9Vまで放電持続時間を測定し、従来
の負極活物質を用いた後述する比較例11の測定値の100
とした指数で示した。結果を第1表に示す。In addition, the battery performance was evaluated using the alkaline manganese battery shown in FIG. 1 with these zinc alloy powders as the negative electrode active material. The alkaline manganese battery of FIG. 1 is composed of a positive electrode can 1, a positive electrode 2, a separator 3, a negative electrode 4 obtained by gelling zinc alloy powder with carboxymethyl cellulose, a negative electrode current collector 5, a rubber packing 6, and a pressing plate 7. . Using this alkaline manganese battery, the discharge duration was measured up to an end voltage of 0.9 V under a discharge negative electrode of 4Ω and a discharge condition of 20 ° C., and the measured value of Comparative Example 11 described below using a conventional negative electrode active material was 100.
It was shown by the index. The results are shown in Table 1.
比較例11 実施例1と同様の方法で亜鉛に水銀を5.0重量%添加
した従来より用いられている汞化亜鉛合金粉末(比較例
11)を得た。これを実施例1と同様の方法で水素ガス発
生試験と電池性能試験を行ない、その結果を第1表に示
した。Comparative Example 11 In the same manner as in Example 1, 5.0% by weight of mercury was added to zinc, which was conventionally used.
11) got. This was subjected to a hydrogen gas generation test and a battery performance test in the same manner as in Example 1, and the results are shown in Table 1.
第1表に示されるごとく、亜鉛にインジウム、タリウム
より選ばれる 1種以上とコバルトとニッケルを特定量添
加して汞化させた汞化亜鉛合金粉末を負極活物質に用い
た実施例1〜8は、比較例1〜10や亜鉛に水銀のみを添
加した従来より用いられている汞化亜鉛合金粉末を負極
活物質に用いた比較例11に比べて、水素ガス発生抑制効
果が大きく、放電性能も優れていることがわかる。 As shown in Table 1, Examples 1 to 8 using zinc halide alloy powder prepared by adding one or more kinds selected from indium and thallium to zinc and a specific amount of cobalt and nickel to make them negative electrode active materials. Compared to Comparative Examples 1 to 10 and Comparative Example 11 in which a zinc halide alloy powder that is conventionally used in which only mercury is added to zinc is used as the negative electrode active material, the hydrogen gas generation suppressing effect is large, and the discharge performance is high. Also proves to be excellent.
(発明の効果) 以上説明のごとく、インジウム、タリウムより選ばれる
1種以上とコバルトとニッケルを特定範囲で含有した亜
鉛合金をそのまま、もしくは汞化して負極活物質として
用いた本発明の亜鉛アルカリ電池は、水素ガス発生率を
抑制しつつ、電池性能を向上させることが可能であり、
また水銀が低含有率もしくは含有しないことから、社会
的ニーズにも沿ったものである。従って、本発明の亜鉛
アルカリ電池は広範な用途に使用可能である。(Effect of the invention) As described above, it is selected from indium and thallium.
The zinc-alkaline battery of the present invention, which is a zinc alloy containing one or more kinds and cobalt and nickel in a specific range as it is, or is used as a negative electrode active material, improves battery performance while suppressing the hydrogen gas generation rate. Is possible
In addition, the low or no content of mercury is in line with social needs. Therefore, the zinc alkaline battery of the present invention can be used in a wide range of applications.
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:正極缶、2:正極、3:セパレーター、4:負極、
5:負極集電体、6:ゴムパッキン、7:押さえ板。FIG. 1 shows a principle diagram of an alkaline manganese battery according to the present invention. 1: positive electrode can, 2: positive electrode, 3: separator, 4: negative electrode,
5: Negative electrode current collector, 6: Rubber packing, 7: Press plate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡崎 良二 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 高田 寛治 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 三浦 晃 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Ryoji Okazaki 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor, Kanji Takada 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. 72) Inventor Akira Miura 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (2)
上を合計0.01〜0.5重量%、コバルトを0.01
〜0.5重量%、ニッケルを0.01〜0.5重量%含
有する亜鉛合金を負極活物質として用いたことを特徴と
する亜鉛アルカリ電池。1. A total of 0.01 to 0.5% by weight of at least one selected from indium and thallium and 0.01 of cobalt.
A zinc-alkaline battery characterized by using a zinc alloy containing 0.5 to 0.5% by weight and 0.01 to 0.5% by weight of nickel as a negative electrode active material.
求の範囲第1項記載の亜鉛アルカリ電池。2. The zinc alkaline battery according to claim 1, wherein the zinc alloy is modified.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60131638A JPH0619993B2 (en) | 1985-06-19 | 1985-06-19 | Zinc alkaline battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60131638A JPH0619993B2 (en) | 1985-06-19 | 1985-06-19 | Zinc alkaline battery |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61290653A JPS61290653A (en) | 1986-12-20 |
JPH0619993B2 true JPH0619993B2 (en) | 1994-03-16 |
Family
ID=15062734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60131638A Expired - Lifetime JPH0619993B2 (en) | 1985-06-19 | 1985-06-19 | Zinc alkaline battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0619993B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5626988A (en) * | 1994-05-06 | 1997-05-06 | Battery Technologies Inc. | Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture |
-
1985
- 1985-06-19 JP JP60131638A patent/JPH0619993B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS61290653A (en) | 1986-12-20 |
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