JPH11265715A - Zinc alloy powder for alkaline battery having little gas generation amount - Google Patents
Zinc alloy powder for alkaline battery having little gas generation amountInfo
- Publication number
- JPH11265715A JPH11265715A JP896599A JP896599A JPH11265715A JP H11265715 A JPH11265715 A JP H11265715A JP 896599 A JP896599 A JP 896599A JP 896599 A JP896599 A JP 896599A JP H11265715 A JPH11265715 A JP H11265715A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- zinc alloy
- zinc
- generation amount
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は改善された特性を持
つアルカリ電池用亜鉛合金粉末に関し、特に熱処理され
たものであることを特徴とするガス発生量の少ない亜鉛
合金粉末に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc alloy powder for an alkaline battery having improved characteristics, and more particularly to a zinc alloy powder which has been subjected to a heat treatment and has a low gas generation amount.
【０００２】[0002]
【従来の技術】従来、アルカリ乾電池等電池の負極材と
しては亜鉛又は亜鉛合金が用いられている。亜鉛は水素
過電圧が高いことや価格が比較的低廉であることから好
んで負極材として用いられてきたのであるが、亜鉛を使
用することのみでは電池使用時における水素ガスの多量
発生を充分に抑制することは困難であってそれに伴う電
解液漏れなどの問題を生じていた。これらの問題を解決
する目的で近年広く行われている有効なガス発生抑制の
方法として亜鉛を汞化することが行われている。しかし
ながら、この方法は廃乾電池を処分する際の深刻な公害
面の問題を伴うものであるため、できるだけ低汞化ある
いは無汞化で所望の効果が得られる亜鉛合金の開発が求
められるようになり、これに応えて本発明者等も特開昭
６３−３０４５７１号公報「電池用亜鉛合金およびその
製造法」において開示したようにそのような亜鉛合金の
開発に一応の成果を上げている。2. Description of the Related Art Conventionally, zinc or a zinc alloy has been used as a negative electrode material for batteries such as alkaline dry batteries. Zinc has been used as a negative electrode material because of its high hydrogen overvoltage and its relatively low price.However, the use of zinc alone sufficiently suppresses the generation of large amounts of hydrogen gas when using batteries. It is difficult to perform such a process, and there has been a problem such as leakage of an electrolytic solution. For the purpose of solving these problems, zinc has been converted into calomel as an effective gas generation suppression method which has been widely used in recent years. However, since this method involves a serious problem of pollution when disposing of the used dry battery, it has been required to develop a zinc alloy that can obtain the desired effect by reducing the amount of calcined or non-melted as much as possible. In response to this, the present inventors have also made a reasonable progress in the development of such a zinc alloy as disclosed in Japanese Patent Application Laid-Open No. Sho 63-304571, entitled "Zinc Alloy for Batteries and Manufacturing Method Thereof".
【０００３】[0003]
【発明が解決しようとする課題】上述のように環境汚染
防止の上からもより一層低汞化あるいは無汞化のもので
ガス発生抑制効果の備わった亜鉛合金の開発が望まれて
いるが、本発明者等の上記公開特許公報にも示されてい
るように水銀の添加量は最低でも 0.3重量％以上でなけ
れば有効な汞化はできないと一般に認識されていたので
あり、アルカリ電池の使用による水素ガス発生抑制の目
的には、ある程度の水銀を添加して汞化した亜鉛合金を
使用することがどうしても必要であると考えられていた
のである。As described above, from the viewpoint of preventing environmental pollution, it is desired to develop a zinc alloy which is further reduced in calorie or has no gasoline and has an effect of suppressing gas generation. As disclosed in the above-mentioned published patent publication of the present inventors, it was generally recognized that effective mercurization could not be achieved unless the amount of mercury added was at least 0.3% by weight or more. It was thought that it was absolutely necessary to use a zinc alloy that had been added with a certain amount of mercury and had been calcined for the purpose of suppressing the generation of hydrogen gas.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するた
め、鋭意研究を続けているうちに、本発明者等は、アル
カリ電池に使用するための亜鉛合金粉末をある条件下で
熱処理することによって水素ガス発生量が熱処理しない
ものに比し著しく少ない改質されたアルカリ電池用亜鉛
合金粉末とすることができることを見い出し本発明を達
成した。Means for Solving the Problems In order to solve the above problems, while continuing intensive research, the present inventors have conducted a heat treatment of a zinc alloy powder for use in an alkaline battery under a certain condition. The present inventors have found that a modified zinc alloy powder for an alkaline battery can be obtained which has a significantly smaller amount of hydrogen gas generation than that of a non-heat-treated hydrogen gas, thereby achieving the present invention.
【０００５】すなわち本発明は電池等の負極材として使
用したときの水素ガスの発生量が従来の亜鉛合金粉末に
比し少なくとも30％少ない新規な亜鉛合金粉末に関し、
アルミニウム、ガリウム、インジウム、タリウム、マグ
ネシウム、カルシウム、ストロンチウム、錫、鉛、ビス
マス、カドミウム、銀及びテルルからなる群より選ばれ
た少なくとも１種の金属を0.0001〜0.5 重量％含み、残
部が亜鉛及び不可避的不純物からなる亜鉛合金粉末であ
って、空気中にアトマイズして製造され、引き続き不活
性ガスあるいは還元性ガス中で熱処理することによっ
て、酸化亜鉛を飽和させた45℃の40%ＫＯＨ溶液中に浸
漬させて測定した水素ガス発生量が、熱処理されていな
いこと以外は同一の亜鉛合金粉末を同一の溶液中に浸漬
させて同一の条件で測定した水素ガス発生量に比し、少
なくとも30％少ないことを特徴とするアルカリ電池用亜
鉛合金粉末に関するものである。That is, the present invention relates to a novel zinc alloy powder that generates at least 30% less hydrogen gas than conventional zinc alloy powder when used as a negative electrode material for batteries and the like.
0.0001 to 0.5% by weight of at least one metal selected from the group consisting of aluminum, gallium, indium, thallium, magnesium, calcium, strontium, tin, lead, bismuth, cadmium, silver and tellurium, with the balance being zinc and inevitable Alloy powder consisting of chemical impurities, produced by atomizing in air, and then heat-treated in an inert gas or reducing gas to obtain a zinc oxide saturated 40% KOH solution at 45 ° C. Hydrogen gas generation measured by immersion is at least 30% less than hydrogen gas generation measured under the same conditions by immersing the same zinc alloy powder in the same solution except that it is not heat-treated The present invention relates to a zinc alloy powder for an alkaline battery.
【０００６】[0006]
【発明の実施の形態】本発明の新規な亜鉛合金粉末は、
合金元素として、アルミニウム、ガリウム、インジウ
ム、タリウム、マグネシウム、カルシウム、ストロンチ
ウム、錫、鉛、ビスマス、カドミウム、銀及びテルルか
らなる群より選ばれた少なくとも１種の金属を0.0001〜
0.5 重量％用い、これを亜鉛及び不可避的不純物と混合
溶融して合金化した亜鉛合金粉末を噴霧法で得た後、熱
処理炉内において100 〜500 ℃の温度条件で熱処理をす
ることによって製造される。この場合の熱処理条件は以
下の通りである。BEST MODE FOR CARRYING OUT THE INVENTION The novel zinc alloy powder of the present invention
As an alloy element, at least one metal selected from the group consisting of aluminum, gallium, indium, thallium, magnesium, calcium, strontium, tin, lead, bismuth, cadmium, silver, and tellurium is 0.0001 to
0.5% by weight, mixed with zinc and unavoidable impurities, melted and alloyed to obtain a zinc alloy powder, and then heat-treated at 100-500 ° C in a heat treatment furnace. You. The heat treatment conditions in this case are as follows.
【０００７】すなわち採用可能な熱処理温度は 100〜50
0 ℃であり、好ましくは 300〜450℃である。これは100
℃以下では、熱処理に時間がかかり過ぎる上に効果が
小さく、又 500℃以上では、亜鉛の融点が420 ℃付近で
あることから合金粉末の一部が溶融して焼結した状態と
なるからである。処理雰囲気は、粉末表面の 酸化を防
止する上で、例えばＨｅ、Ｎｅ、Ｈ2、ＣＯ、ＮＨ3等の
不活性ガスあるいは還元性ガスとする。熱処理時間は、
５分〜５時間とすることができるが、１〜２時間が好ま
しい。That is, the heat treatment temperature that can be employed is 100 to 50
0 ° C, preferably 300-450 ° C. This is 100
If the temperature is lower than ℃, the heat treatment takes too much time and the effect is small.If it is higher than 500 ° C, the melting point of zinc is around 420 ° C, so that part of the alloy powder is melted and sintered. is there. The treatment atmosphere is, for example, an inert gas such as He, Ne, H 2 , CO, or NH 3 or a reducing gas in order to prevent oxidation of the powder surface. The heat treatment time is
It can be from 5 minutes to 5 hours, preferably from 1 to 2 hours.
【０００８】本発明で使用する熱処理炉としては、所定
の雰囲気を保ち得るものであればどのような構造のもの
でもよく、又、加熱源としては電気、液体、気体、固体
その他どのような加熱源を用いてもよい。従来技術では
上述組成の合金を通常のアトマイズ法によって製造し、
汞化処理することによってアルカリ電池用亜鉛合金粉末
を製造しているが、この方法ではアトマイズ粉末製造時
に亜鉛粉末が急冷され且つ、アトマイズに空気が用いら
れる為、粉末表面に酸化皮膜が生じ、得られた亜鉛合金
粉末は多結晶であって添加金属も多くは偏析して存在す
るものとなる。この為、亜鉛合金粉末のガス発生を抑制
する目的で加えた添加金属の効果は薄れることとなり、
更に、亜鉛合金粉末の表面に生じた酸化物層を除去する
為の工程が必要となっていた。The heat treatment furnace used in the present invention may have any structure as long as it can maintain a predetermined atmosphere. The heating source may be electricity, liquid, gas, solid or any other heating source. A source may be used. In the prior art, an alloy having the above composition is manufactured by a normal atomizing method,
The zinc alloy powder for alkaline batteries is produced by the treatment with calomelization. However, in this method, the zinc powder is rapidly cooled at the time of producing the atomized powder, and air is used for atomizing. The obtained zinc alloy powder is polycrystalline, and many of the added metals are segregated. For this reason, the effect of the added metal added for the purpose of suppressing the gas generation of the zinc alloy powder is weakened,
Further, a step for removing an oxide layer generated on the surface of the zinc alloy powder has been required.
【０００９】これに対し、本発明法では不活性ガスある
いは還元性ガス雰囲気中所定温度条件下で熱処理を行な
う為、製造された亜鉛合金粉末は結晶が均一で、安定し
ており、亜鉛合金粉末表面に酸化物層ができていても上
述の雰囲気処理で十分に除去できるため、従来法では必
要であった酸化物除去工程を設ける必要がない。又、製
造された亜鉛合金粉末は電池負極材として使用された場
合等におけるガス発生量が著しく少ないものであること
が確認された。On the other hand, in the method of the present invention, since the heat treatment is performed under a predetermined temperature condition in an atmosphere of an inert gas or a reducing gas, the produced zinc alloy powder has a uniform crystal and is stable. Even if an oxide layer is formed on the surface, the oxide layer can be sufficiently removed by the above-described atmosphere treatment, so that it is not necessary to provide an oxide removing step which is necessary in the conventional method. In addition, it was confirmed that the produced zinc alloy powder produced a remarkably small amount of gas when used as a battery negative electrode material.
【００１０】この効果は極めて顕著であるため、本発明
の亜鉛合金粉末を同定する手段として用いることができ
る。即ち、たとえば与えられた亜鉛合金粉末を、酸化亜
鉛を飽和させた45℃の40％ＫＯＨ水溶液中に浸漬させて
測定した水素ガス発生量が、同じ組成の熱処理されてい
ない従来の亜鉛合金粉末を同一の酸化亜鉛飽和溶液中に
浸漬させて同一の条件で測定した水素ガスの発生量に比
し、少なくとも30％少ないことが確認されれば、それは
与えられた粉末が熱処理された本発明の亜鉛合金粉末で
あることを意味すると結論してよい。何故なら、従来、
そのように改質された亜鉛合金粉末は存在しなかったか
らである。以下、本発明を実施例により詳細に説明す
る。Since this effect is extremely remarkable, it can be used as a means for identifying the zinc alloy powder of the present invention. That is, for example, a given zinc alloy powder is immersed in a 40% KOH aqueous solution at 45 ° C. saturated with zinc oxide, and the hydrogen gas generation amount measured is the same as that of a conventional zinc alloy powder having the same composition but not heat-treated. If it is confirmed that the given powder is at least 30% less than the amount of hydrogen gas generated by immersing in the same zinc oxide saturated solution and measuring under the same conditions, it means that the given powder is heat-treated zinc of the present invention. It may be concluded that this means an alloy powder. Because conventionally,
This is because there was no zinc alloy powder modified as such. Hereinafter, the present invention will be described in detail with reference to examples.
【００１１】[0011]
【実施例１】表１に示す組成の各種亜鉛合金を、通常の
噴霧法により粒度48〜150 メッシュの粉末として製造
し、次いでこれらの粉末を熱処理炉中にてＨ2ガス雰囲
気下 350℃で２時間熱処理し、得られた熱処理済み亜鉛
合金粉末の一定量をＫＯＨ溶液中に入れ、水銀を0.04重
量％添加して汞化したもの（表中偶数番号の合金粉末）
と、無汞化のもの （同奇数番号の合金粉末）を、それ
ぞれ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
を表1に示す。水素ガス発生量（μl／g.d）は合金粉末
１ｇ当り１日の発生量である。同様に表1に示した各組
成の汞化した又はしない亜鉛合金粉末を熱処理しないこ
と以外は、上述と同じ方法で評価試験した結果を熱処理
品の結果と対比して表1に示した。Example 1 Various zinc alloys having the compositions shown in Table 1 were produced as powders having a particle size of 48 to 150 mesh by a usual spraying method, and then these powders were heated at 350 ° C. in a H 2 gas atmosphere in a heat treatment furnace. Heat treated for 2 hours, put a certain amount of the obtained heat treated zinc alloy powder in KOH solution, add 0.04% by weight of mercury, and make it calomelized (even numbered alloy powder in the table)
And anodized material (alloy powder of the same odd number) 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 shown in Table 1. The amount of hydrogen gas generated (μl / gd) is the amount of hydrogen gas generated per day per g of alloy powder. Similarly, the results of evaluation tests performed in the same manner as described above, except that the heat-treated zinc alloy powder having or without the respective compositions shown in Table 1 was not heat-treated, are shown in Table 1 in comparison with the results of the heat-treated products.
【００１２】これらの結果から同じ組成の亜鉛合金粉末
で あっても熱処理品は非熱処理品に比べ水素ガス発生
量がほぼ半分位に抑制されることが判明した。即ち、無
汞化の亜鉛合金粉末であっても熱処理品（奇数番号例）
は、従来の非熱処理低汞化亜鉛合金粉末とほぼ同等の水
素ガス発生量であり、従来の低水銀電池の代替品として
無水銀電池を製造、使用することが充分可能となったこ
とが理解される。From these results, it was found that even with the zinc alloy powder having the same composition, the amount of hydrogen gas generated in the heat-treated product was suppressed to about half that of the non-heat-treated product. In other words, heat-treated products (odd-numbered examples) even for non-melonized zinc alloy powders
Shows that the amount of hydrogen gas generated is almost the same as that of the conventional non-heat-treated low-melting zinc alloy powder, and that it is now possible to manufacture and use mercury-free batteries as alternatives to conventional low-mercury batteries. Is done.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【実施例２】鉛0.05％、マグネシウム 0.007％、残部が
亜鉛及び不可避的不純物からなる組成の亜鉛合金粉末を
供試材として、表示の各条件下で熱処理した場合としな
い場合について、水素ガス発生量を調べた結果を表２に
示す。Example 2 Hydrogen gas generation was conducted with and without heat treatment under the indicated conditions using a zinc alloy powder having a composition consisting of 0.05% lead, 0.007% magnesium, and the balance consisting of zinc and unavoidable impurities. Table 2 shows the results of the determination.
【００１５】[0015]
【表２】 [Table 2]
【００１６】表２から、熱処理を行うためのガス雰囲気
としてはＨ2ガスの方がＮ2ガスより、水素ガス抑制効果
を高める目的上、若干優れていることが理解される。た
だし、どんなガス雰囲気とすることが最も有利であるか
は製造コストに合わせて調整できることが理解される。From Table 2, it is understood that H 2 gas is slightly superior to N 2 gas as a gas atmosphere for performing the heat treatment for the purpose of enhancing the hydrogen gas suppressing effect. However, it is understood that the most advantageous gas atmosphere can be adjusted according to the production cost.
【００１７】[0017]
【発明の効果】本発明によれば、上述の如く、汞化され
た又は汞化されていない亜鉛合金粉末を簡易な手段で熱
処理することのみによって電池の負極材として使用した
ときなどの水素ガス発生量を従来品に比し著しく減少さ
せることができるばかりでなく、無汞化の亜鉛合金粉末
を用いた場合でさえも、従来の低汞化亜鉛合金粉末と同
等程度に電池負極材として使用したときなどの水素ガス
発生量を抑制できるので無汞化亜鉛合金粉末を用いた電
池即ち無水銀電池としても充分使用できる電池がつくれ
ることになり、公害面における利点ははかり知れない程
大であるということができる。According to the present invention, as described above, hydrogen gas, such as when used as a negative electrode material of a battery by only heat-treating a zinc alloy powder that has been calorinized or not, by simple means, is used. Not only can the generation amount be significantly reduced compared to conventional products, but even when non-melonized zinc alloy powder is used, it is used as a battery negative electrode material to the same extent as conventional low-melonized zinc alloy powder Since the amount of generated hydrogen gas can be suppressed, for example, a battery using a non-melonized zinc alloy powder, that is, a battery that can be sufficiently used as a mercury-free battery, can be produced, and the advantage in terms of pollution is enormous. It can be said.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高岡 衛 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Mamoru Takaoka 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd.
Claims (1)
タリウム、マグネシウム、カルシウム、ストロンチウ
ム、錫、鉛、ビスマス、カドミウム、銀及びテルルから
なる群より選ばれた少なくとも１種の金属を0.0001〜0.
5 重量％含み、残部が亜鉛及び不可避的不純物からなる
亜鉛合金粉末であって、空気中にアトマイズして製造さ
れ、引き続き不活性ガスあるいは還元性ガス中で熱処理
することによって、酸化亜鉛を飽和させた45℃の40%Ｋ
ＯＨ溶液中に浸漬させて測定した水素ガス発生量が、熱
処理されていないこと以外は同一の亜鉛合金粉末を同一
の溶液中に浸漬させて同一の条件で測定した水素ガス発
生量に比し、少なくとも30％少ないことを特徴とするア
ルカリ電池用亜鉛合金粉末。1. An aluminum, gallium, indium,
Thallium, magnesium, calcium, strontium, tin, lead, bismuth, cadmium, silver and at least one metal selected from the group consisting of tellurium is 0.0001-0.
A zinc alloy powder containing 5% by weight, with the balance being zinc and unavoidable impurities, manufactured by atomizing in air, and subsequently heat-treating in an inert gas or a reducing gas to saturate the zinc oxide. 40% K at 45 ℃
The amount of hydrogen gas generated by immersion in the OH solution was compared to the amount of hydrogen gas generated by immersing the same zinc alloy powder in the same solution and measuring under the same conditions except that the heat treatment was not performed, Zinc alloy powder for alkaline batteries, characterized by at least 30% less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP896599A JP3352965B2 (en) | 1999-01-18 | 1999-01-18 | Zinc alloy powder for alkaline batteries with low gas generation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP896599A JP3352965B2 (en) | 1999-01-18 | 1999-01-18 | Zinc alloy powder for alkaline batteries with low gas generation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1193690A Division JP2932285B2 (en) | 1989-07-26 | 1989-07-26 | Method for producing zinc alloy powder for alkaline batteries with low gas generation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11265715A true JPH11265715A (en) | 1999-09-28 |
| JP3352965B2 JP3352965B2 (en) | 2002-12-03 |
Family
ID=11707403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP896599A Expired - Lifetime JP3352965B2 (en) | 1999-01-18 | 1999-01-18 | Zinc alloy powder for alkaline batteries with low gas generation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3352965B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001091224A1 (en) * | 2000-05-24 | 2001-11-29 | Eveready Battery Company, Inc. | Zero mercury air cell |
| JP2005216791A (en) * | 2004-02-02 | 2005-08-11 | Napura:Kk | Electromagnetic wave absorbing and shielding material |
| WO2006047917A1 (en) * | 2004-11-05 | 2006-05-11 | Chung Pak Battery Works Ltd. | Negative electrode of dry battery, manufacture method of the same, and zinc-manganese dry battery using the same |
| WO2006053465A1 (en) * | 2004-11-16 | 2006-05-26 | Chung Pak Battery Works Ltd. | Zinc particles for zinc-manganese dry battery and manufacture method of the same |
| WO2006053466A1 (en) * | 2004-11-16 | 2006-05-26 | Chung Pak Battery Works Ltd. | Zinc plate for zinc-manganese dry battery and forming method of the same |
| CN100373669C (en) * | 2006-06-02 | 2008-03-05 | 浙江大学 | Alkaline zinc-based secondary battery negative electrode material and its preparing method |
| CN105014088A (en) * | 2015-08-18 | 2015-11-04 | 云南驰宏锌锗股份有限公司 | Preparing method for high-aluminum pentabasic alloy zinc powder for purification |
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| JP2006032152A (en) * | 2004-07-16 | 2006-02-02 | Fdk Energy Co Ltd | Cylindrical alkaline battery |
| CN102274935A (en) * | 2011-07-15 | 2011-12-14 | 云南大泽电极科技有限公司 | Horizontal continuous casting manufacturing method of lead alloy plates |
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1999
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001091224A1 (en) * | 2000-05-24 | 2001-11-29 | Eveready Battery Company, Inc. | Zero mercury air cell |
| US6602629B1 (en) | 2000-05-24 | 2003-08-05 | Eveready Battery Company, Inc. | Zero mercury air cell |
| JP2005216791A (en) * | 2004-02-02 | 2005-08-11 | Napura:Kk | Electromagnetic wave absorbing and shielding material |
| JP4553180B2 (en) * | 2004-02-02 | 2010-09-29 | 有限会社ナプラ | Electromagnetic wave absorption shielding material |
| WO2006047917A1 (en) * | 2004-11-05 | 2006-05-11 | Chung Pak Battery Works Ltd. | Negative electrode of dry battery, manufacture method of the same, and zinc-manganese dry battery using the same |
| WO2006053465A1 (en) * | 2004-11-16 | 2006-05-26 | Chung Pak Battery Works Ltd. | Zinc particles for zinc-manganese dry battery and manufacture method of the same |
| WO2006053466A1 (en) * | 2004-11-16 | 2006-05-26 | Chung Pak Battery Works Ltd. | Zinc plate for zinc-manganese dry battery and forming method of the same |
| CN100373669C (en) * | 2006-06-02 | 2008-03-05 | 浙江大学 | Alkaline zinc-based secondary battery negative electrode material and its preparing method |
| CN105014088A (en) * | 2015-08-18 | 2015-11-04 | 云南驰宏锌锗股份有限公司 | Preparing method for high-aluminum pentabasic alloy zinc powder for purification |
| CN105014088B (en) * | 2015-08-18 | 2017-05-31 | 云南驰宏锌锗股份有限公司 | It is a kind of to purify with the preparation method of high alumina quinary alloy zinc powder |
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| JP3352965B2 (en) | 2002-12-03 |
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