JPS63171842A - Zinc alloy for battery and its production - Google Patents
Zinc alloy for battery and its productionInfo
- Publication number
- JPS63171842A JPS63171842A JP62003828A JP382887A JPS63171842A JP S63171842 A JPS63171842 A JP S63171842A JP 62003828 A JP62003828 A JP 62003828A JP 382887 A JP382887 A JP 382887A JP S63171842 A JPS63171842 A JP S63171842A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- zinc alloy
- mercury
- aluminum
- alloy
- 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
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 7
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- -1 indium-lead-aluminum-zinc Chemical compound 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZULTYUIALNTCSA-UHFFFAOYSA-N zinc hydride Chemical compound [ZnH2] ZULTYUIALNTCSA-UHFFFAOYSA-N 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
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】
〔産業上の利用分野〕
本発明は電解液中で水素ガス発生量が少ないガリウム−
鉛−アルミニウムー亜鉛系またはインジウム−鉛−アル
ミニウムー亜鉛系合金からなる電池用亜鉛合金およびそ
の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention uses gallium, which generates a small amount of hydrogen gas in an electrolyte.
The present invention relates to a zinc alloy for batteries made of a lead-aluminum-zinc alloy or an indium-lead-aluminum-zinc alloy, and a method for producing the same.
従来アルカリ乾電池等の電池の負極材として亜鉛または
亜鉛合金が用いられている。亜鉛は水素過電圧や価格の
面から好んで用いられてきたものであるが、それのみで
は電池の使用時や保存中の水素ガスの多量発生を抑制し
切れず、それに起因して電池からの電解液漏れなどの問
題を生じるものである。Zinc or zinc alloy has conventionally been used as a negative electrode material for batteries such as alkaline dry batteries. Zinc has been preferred from the viewpoint of hydrogen overvoltage and cost, but zinc alone cannot suppress the generation of large amounts of hydrogen gas during battery use and storage, and due to this, the electrolysis from the battery This causes problems such as liquid leakage.
近年このようなガス発生の抑制のための技術改良として
亜鉛の汞化が行なわれ、さらに廃乾電池の処分等に間す
る公害面の懸念から低汞化ないし無汞化のための亜鉛合
金の開発が行なわれるようになってきている。このよう
な亜鉛合金としてはたとえばガリウム−インジウム−亜
鉛系合金などが知られている（特開昭６０−１１４５４
８、特開昭６ｌ−２５３３３９） 。In recent years, as a technological improvement to suppress the generation of such gases, zinc has been converted into hydrogen, and due to concerns about pollution during the disposal of waste dry batteries, zinc alloys have been developed to reduce or eliminate hydrogen. is increasingly being carried out. As such a zinc alloy, for example, a gallium-indium-zinc alloy is known (Japanese Patent Laid-Open No. 11454/1983).
8, Japanese Patent Publication No. 61-253339).
しかし、それらの亜鉛合金によるガス発生の抑制効果は
ある程度評価されるものの、現状では必ずしも満足され
得るものではなく、さらに安定してガス発生量の少ない
電池用の低汞化亜鉛合金が求められている。However, although the effectiveness of these zinc alloys in suppressing gas generation has been evaluated to some extent, they are not necessarily satisfactory at present, and there is a need for more stable, low-rate zinc alloys for batteries that generate less gas. There is.
従って本発明の目的は、安定的に水素ガス発生率がより
低く、かつ含有水銀量が３％以下の電池用低汞化亜鉛合
金を得ることにある。Therefore, an object of the present invention is to obtain a low-fragility zinc alloy for batteries, which stably has a lower hydrogen gas generation rate and has a mercury content of 3% or less.
上記目的を達成するため、本発明は重量％においてガリ
ウムまたはインジウム０．００１〜０．２％、鉛０．０
１〜０．６％、アルミニウム０．００１〜０．１％およ
び−水銀０．５〜３．０％を含み残部が亜鉛および不可
避的不純物からなる電池用亜鉛合金を提供するものであ
り、またこのような亜鉛合金を得るために予め調製した
ガリウムまたはインジウム、並びに鉛およびアルミニウ
ムを含む亜鉛合金に水銀を添加し汞化せしめるような方
法またはガリウムまたはインジウムのいずれか、並びに
鉛および亜鉛の何れか１種または２種以上の混合成分を
予め水銀で汞化させ、次いでこれを亜鉛−アルミニウム
合金または前記合金成分の残部を含む亜鉛−アルミニウ
ム合金に添加する方法を提案するものである。In order to achieve the above object, the present invention provides 0.001 to 0.2% of gallium or indium and 0.0% of lead by weight.
1 to 0.6% of aluminum, 0.001 to 0.1% of aluminum, and 0.5 to 3.0% of mercury, the balance being zinc and unavoidable impurities; To obtain such a zinc alloy, gallium or indium prepared in advance, and a method of adding mercury to a zinc alloy containing lead and aluminum to form a hydrogen atom, or either gallium or indium, or either lead or zinc. The present invention proposes a method in which one or more mixed components are preliminarily oxidized with mercury, and then added to a zinc-aluminum alloy or a zinc-aluminum alloy containing the remainder of the above-mentioned alloy components.
本発明において、ガリウムまたはインジウムの含有量は
０．００１〜０．２％、鉛の含有量は０．０１〜０，６
％、およびアルミニウムの含有量は０．００１〜０．１
％が必要であり、上記の下限未満では水素ガス発生の抑
制効果が不十分であり、また上記の上限値を超えてもそ
れ以上の効果は得られないか、またはガス発生の抑制効
果が逆に劣化することが認められている。In the present invention, the content of gallium or indium is 0.001 to 0.2%, and the content of lead is 0.01 to 0.6%.
%, and the aluminum content is 0.001-0.1
%, and if it is less than the above lower limit, the effect of suppressing hydrogen gas generation will be insufficient, and even if it exceeds the above upper limit, no further effect will be obtained, or the effect of suppressing gas generation will be reversed. It is recognized that the deterioration occurs.
また水銀の使用量は０．５〜３．０％が必要であり、好
ましくは０．５〜２．０％であって、０．５％未満にな
ると水素ガス発生量が急激に増加し、３．０％以上にな
ってもガス発生量の抑制効果は余り変らない。In addition, the amount of mercury used must be 0.5 to 3.0%, preferably 0.5 to 2.0%, and if it is less than 0.5%, the amount of hydrogen gas generated will increase rapidly. Even if it exceeds 3.0%, the effect of suppressing the amount of gas generated does not change much.
すなわち本合金において、従来の６〜１０％水銀を含む
汞化亜鉛に比較し十分に低汞化の目的が達し得られるこ
とが見出されたものである。That is, it has been found that this alloy can sufficiently achieve the purpose of lowering the mercury compared to the conventional zinc hydride containing 6 to 10% mercury.
なおガリウムまたはインジウム並びに、鉛、アルミニウ
ムそして水銀の何れか１成分でも欠く場合は所定の効果
が発揮され得ない。Note that if any one of gallium or indium, lead, aluminum, and mercury is missing, the desired effect cannot be achieved.
本発明の亜鉛合金の製造は、上記成分組成を有するガリ
ウム−鉛−アルミニウムー亜鉛合金またはインジウム−
鉛−アルミニウムー亜鉛合金を得てこれに所定の水銀を
添加し混合させて汞化せしめる方法またはガリウムまた
はインジウム並びに、鉛、および亜鉛のうち１種または
２種以上の金属を予め水銀と混合させた後、亜鉛−アル
ミニウム合金あるいは残部の合金成分を含む亜鉛−アル
ミニウム合金に添加する方法によって行なわれる。The zinc alloy of the present invention can be manufactured by using a gallium-lead-aluminum-zinc alloy or an indium-lead-aluminum alloy having the above-mentioned composition.
A method in which a lead-aluminum-zinc alloy is obtained, a specified amount of mercury is added thereto, and the mixture is made to form a hydrogen atom, or one or more metals selected from gallium or indium, lead, and zinc are mixed with mercury in advance. After that, it is added to the zinc-aluminum alloy or the zinc-aluminum alloy containing the remaining alloy components.
これにより汞化が均一にかつ効率的に行なわれそれによ
って電池用亜鉛合金としての水素ガス発生の抑制効果が
十分なものとなる。As a result, hydrogenation is uniformly and efficiently carried out, and as a result, the zinc alloy for batteries has a sufficient effect of suppressing hydrogen gas generation.
〔実施例１〕
噴霧法で製造された粒度４８〜１５０メツシユのガリウ
ム−鉛−アルミニウムー亜鉛合金粉を７０℃の１０％Ｋ
ＯＨ溶液内で水銀を滴下混合させることによって汞化さ
せ、第１表に試料１および２として示す本発明組成の亜
鉛合金を得た。[Example 1] Gallium-lead-aluminum-zinc alloy powder with a particle size of 48 to 150 mesh produced by a spraying method was heated to 10% K at 70°C.
Zinc alloys having the compositions of the present invention shown as Samples 1 and 2 in Table 1 were obtained by dropwise mixing mercury in an OH solution.
また予め成分金属粉の１種または２種を水銀と混合した
ものを７０℃の１０％ＫＯＨ溶液中に滴下させて亜鉛−
アルミニウム合金粉または亜鉛−鉛一アルミニウム合金
粉に混合汞化させ、第１表に試料３〜５として示す本発
明組成の亜鉛合金を得た。In addition, one or two of the component metal powders mixed with mercury were dropped into a 10% KOH solution at 70°C to remove zinc.
Aluminum alloy powder or zinc-lead-aluminum alloy powder was mixed into a slurry to obtain zinc alloys having the compositions of the present invention shown as Samples 3 to 5 in Table 1.
次にこれら亜鉛合金粉を、酸化亜鉛を飽和させた４５℃
の４０％ＫＯＨ溶液中に浸漬させて水素ガス発生量を測
定し評価した。その結果を第１表に併せて示した。Next, these zinc alloy powders were heated at 45℃ saturated with zinc oxide.
It was evaluated by immersing it in a 40% KOH solution and measuring the amount of hydrogen gas generated. The results are also shown in Table 1.
第１表
〔比較例〕
合金組成を本発明組成範囲外としたほかは前記実施例と
同じ方法によって製造された亜鉛合金粉を未化させて第
２表に試料６〜８として示す汞化亜鉛合金粉を得た。Table 1 [Comparative Example] Zinc alloy powder produced by the same method as in the above example except that the alloy composition was outside the composition range of the present invention was unconsolidated and is shown as Samples 6 to 8 in Table 2. An alloy powder was obtained.
次にこれら亜鉛合金粉を前記実施例と同じ方法によって
水素ガス発生量を測定し評価しな、その結果を第２表に
併せて示した。Next, these zinc alloy powders were evaluated by measuring the amount of hydrogen gas generated by the same method as in the above example, and the results are also shown in Table 2.
第２表
以上のとおり、比較例の試料における水素ガス発生量が
約２μｌ／日・ｇであるのに対し本発明合金の実施例試
料におけるそれは約１μｌ／日・３であって明らかに改
善されている。As shown in Table 2 above, the amount of hydrogen gas generated in the comparative sample was approximately 2 μl/day·g, while that in the example sample of the invention alloy was approximately 1 μl/day·3, which was clearly improved. ing.
〔実施例２〕
噴霧法で製造された粒度４８〜１５０メツシユのインジ
ウム−鉛−アルミニウムー亜鉛合金粉を７０℃の１０％
ＫＯＨ溶液中で水銀を滴下混合させることによって未化
させ、第３表に試ｆ！１１０〜１４として示す本発明組
成の亜鉛合金を得た。[Example 2] Indium-lead-aluminum-zinc alloy powder with a particle size of 48 to 150 mesh produced by a spraying method was heated to 10% at 70°C.
Mercury was sterilized by dropwise mixing in a KOH solution, and the test results are shown in Table 3. Zinc alloys having compositions of the present invention shown as 110-14 were obtained.
また予め成分金属粉の１種または２種以上を水銀と混合
したものを７０℃の１０％ＫＯＨ溶液中に滴下させて亜
鉛−アルミニウム金金粉または成分金属の残余を含む亜
鉛−アルミニウム舎金粉に混合汞化させ、第３表に試料
１５〜２３として示す本発明組成の亜鉛合金を得た。In addition, one or more component metal powders mixed with mercury are dropped into a 10% KOH solution at 70°C and mixed with zinc-aluminum gold powder or zinc-aluminum metal powder containing the remainder of the component metals. The zinc alloys having the compositions of the present invention shown as Samples 15 to 23 in Table 3 were obtained.
次にこれら亜鉛合金粉を酸化亜鉛を飽和させた４５℃の
４０％ＫＯＨ溶液中に浸漬させて水素ガス発生量を測定
し評価した。その結果を第３表に併せて示した。Next, these zinc alloy powders were immersed in a 40% KOH solution at 45° C. saturated with zinc oxide, and the amount of hydrogen gas generated was measured and evaluated. The results are also shown in Table 3.
第３表
本０．０５％分だけ水銀中に添加
〔比較例〕
合金組成を本発明組成範囲外としたほかは前記実施例２
と同じ方法によって製造された亜鉛合金粉を汞化させて
第４表に試料２４〜２８として示した汞化亜鉛合金粉を
得た。Table 3 Added 0.05% of mercury to mercury [Comparative example] Example 2 above except that the alloy composition was outside the composition range of the present invention
Zinc alloy powders produced in the same manner as above were subjected to filtration to obtain filtrated zinc alloy powders shown as Samples 24 to 28 in Table 4.
次にこれら亜鉛合金粉を前記実施例と同じ方法によって
水素ガス発生量を測定し評価した。その結果を第４表に
併せて示した。Next, these zinc alloy powders were evaluated by measuring the amount of hydrogen gas generated by the same method as in the above example. The results are also shown in Table 4.
第４表
以上のように、比較例の試料における水素ガス発生量が
約２μｌ／日・３以上であるのに対し本発明合金の実施
例試料におけるそれは安定的に約１μｌ／日・２であっ
て明らかに改善されている。As shown in Table 4 above, the amount of hydrogen gas generated in the comparative sample was about 2 μl/day.3 or more, whereas the amount of hydrogen gas generated in the example sample of the alloy of the present invention was stably about 1 μl/day.2. It has clearly been improved.
本発明組成の電池用亜鉛合金およびその製造法によって
電池電解液中における水素ガス発生量を安定的に従来よ
りもさらに低減させることが可能となった。By using the zinc alloy for batteries having the composition of the present invention and the method for producing the same, it has become possible to stably reduce the amount of hydrogen gas generated in the battery electrolyte more than ever before.
Claims (3)
００１〜０．２％、鉛０．０１〜０．６％、アルミニウ
ム０．００１〜０．１％および水銀０．５〜３．０％を
含み、残部が亜鉛および不可避的不純物からなることを
特徴とする電池用亜鉛合金。(1) Gallium or indium 0.0% by weight.
001-0.2%, lead 0.01-0.6%, aluminum 0.001-0.1% and mercury 0.5-3.0%, with the balance consisting of zinc and unavoidable impurities. Characteristic zinc alloy for batteries.
よびアルミニウムを含む亜鉛合金に、水銀を添加し汞化
せしめることによってガリウムまたはインジウム０．０
０１〜０．２％、鉛０．０１〜０．６％、アルミニウム
０．００１〜０．１％および水銀０．５〜３．０％を含
み、残部が亜鉛および不可避的不純物からなる亜鉛合金
を得ることを特徴とする電池用亜鉛合金の製造方法。(2) By adding mercury to a zinc alloy containing either gallium or indium, lead and aluminum, and making it aqueous, 0.0% of gallium or indium is added.
Zinc alloy containing 0.01 to 0.2%, lead 0.01 to 0.6%, aluminum 0.001 to 0.1%, and mercury 0.5 to 3.0%, with the balance consisting of zinc and inevitable impurities. A method for producing a zinc alloy for batteries, characterized in that it obtains the following:
、鉛および亜鉛のうち１種または２種以上を水銀で汞化
し、次いで亜鉛−アルミニウム合金または残部の金属成
分を含む亜鉛−アルミニウム合金に混合せしめてガリウ
ムまたはインジウム０．００１〜０．２％、鉛０．０１
〜０．６％、アルミニウム０．００１〜０．１％および
水銀０．５〜３．０％を含み残部が亜鉛および不可避的
不純物からなる亜鉛合金を得ることを特徴とする電池用
亜鉛合金の製造方法。(3) Either one of gallium or indium and one or more of lead and zinc are oxidized with mercury, and then mixed with a zinc-aluminum alloy or a zinc-aluminum alloy containing the remaining metal components to form gallium. Or indium 0.001-0.2%, lead 0.01
~0.6% aluminum, 0.001~0.1% aluminum, and 0.5~3.0% mercury, the balance being zinc and inevitable impurities. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62003828A JPS63171842A (en) | 1987-01-10 | 1987-01-10 | Zinc alloy for battery and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62003828A JPS63171842A (en) | 1987-01-10 | 1987-01-10 | Zinc alloy for battery and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63171842A true JPS63171842A (en) | 1988-07-15 |
Family
ID=11568058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62003828A Pending JPS63171842A (en) | 1987-01-10 | 1987-01-10 | Zinc alloy for battery and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63171842A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5994371A (en) * | 1982-11-22 | 1984-05-31 | Mitsui Mining & Smelting Co Ltd | Alkaline battery and its manufacturing method |
| JPS60175368A (en) * | 1984-02-20 | 1985-09-09 | Matsushita Electric Ind Co Ltd | Zinc-alkaline primary cell |
| JPS61253339A (en) * | 1985-05-02 | 1986-11-11 | Toho Aen Kk | Zinc alloy for battery electrode |
| JPS62123653A (en) * | 1985-11-25 | 1987-06-04 | Mitsui Mining & Smelting Co Ltd | Zinc-alkaline battery |
-
1987
- 1987-01-10 JP JP62003828A patent/JPS63171842A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5994371A (en) * | 1982-11-22 | 1984-05-31 | Mitsui Mining & Smelting Co Ltd | Alkaline battery and its manufacturing method |
| JPS60175368A (en) * | 1984-02-20 | 1985-09-09 | Matsushita Electric Ind Co Ltd | Zinc-alkaline primary cell |
| JPS61253339A (en) * | 1985-05-02 | 1986-11-11 | Toho Aen Kk | Zinc alloy for battery electrode |
| JPS62123653A (en) * | 1985-11-25 | 1987-06-04 | Mitsui Mining & Smelting Co Ltd | Zinc-alkaline battery |
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