JP3343803B2 - Zinc alloy powder for alkaline battery and method for producing the same - Google Patents
Zinc alloy powder for alkaline battery and method for producing the sameInfo
- Publication number
- JP3343803B2 JP3343803B2 JP14130295A JP14130295A JP3343803B2 JP 3343803 B2 JP3343803 B2 JP 3343803B2 JP 14130295 A JP14130295 A JP 14130295A JP 14130295 A JP14130295 A JP 14130295A JP 3343803 B2 JP3343803 B2 JP 3343803B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- alloy powder
- zinc alloy
- weight
- battery
- 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
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Classifications
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ電池の負極活
物質となる亜鉛合金粉末およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc alloy powder used as a negative electrode active material for an alkaline battery and a method for producing the same.
【０００２】[0002]
【従来の技術】電解液が苛性カリや苛性ソーダのような
アルカリ溶液であるアルカリ電池の負極として使用され
るアルカリ電池用亜鉛合金粉末は、電気亜鉛あるいは蒸
留亜鉛のような工業的に得られる亜鉛を原料とし、少量
の添加金属で合金化した溶湯をアトマイズ法で噴霧して
製造している。亜鉛合金粉末については過去数々の技術
改良が加えられ現在水銀無添加の無汞化粉が用いられて
いる。2. Description of the Related Art A zinc alloy powder for an alkaline battery used as a negative electrode of an alkaline battery in which an electrolytic solution is an alkaline solution such as caustic potash or caustic soda is made of industrial zinc such as electric zinc or distilled zinc. It is manufactured by spraying a molten alloy alloyed with a small amount of additive metal by an atomizing method. Many technical improvements have been made in the past on zinc alloy powder, and mercury-free non-melted powder is now used.
【０００３】改良技術については以下の引用例がある。
例えば原料亜鉛中の不可避不純物や製造工程において使
用する器具・器材から微量混入する不純物としてＦｅ、
Ｎｉ、Ｃｏその他の不純物がある。これらは電池におい
ては亜鉛の腐食を促すものであってガス発生増となるの
で、その対策として特開昭５９−３３７５７では「ガス
発生をまねく不純物が鉄、ニッケル、コバルト等の強磁
性体であり、これらが最も混入しやすい物質であるの
で」とし磁束密度１５，０００ガウス以上の強磁場中で
磁選することにより耐漏液性に優れた電池の製造方法を
開示している。また、特開昭６１−６１３６５には「一
般に２種以上の金属が接すると局部電池をつくり、水溶
液中で接した場合、水の分解を行いガスが発生するとい
う問題点がある。特に鉄、ニッケル等はアルカリ液中で
亜鉛粉と接すると多量のガスが発生し、また鉄、ニッケ
ルは水銀に汞化されないため、水銀汞化した亜鉛粉との
接触でも多量のガスが発生して好ましくない。」との記
載があり集電体を鉛とする改良技術を開示している。[0003] There are the following cited examples of improved techniques.
For example, Fe, as an unavoidable impurity in the raw material zinc, or a trace amount of impurities mixed from tools and equipment used in the manufacturing process,
There are Ni, Co and other impurities. These batteries promote the corrosion of zinc in a battery and increase gas generation, and as a countermeasure, JP-A-59-33757 states that impurities that cause gas generation are ferromagnetic substances such as iron, nickel, and cobalt. Since these are the substances which are most likely to be mixed, a method of manufacturing a battery having excellent liquid leakage resistance by performing magnetic separation in a strong magnetic field having a magnetic flux density of 15,000 gauss or more is disclosed. Japanese Patent Application Laid-Open No. 61-61365 discloses that "in general, a local battery is formed when two or more metals come into contact with each other, and when they come into contact with an aqueous solution, water is decomposed to generate gas. Nickel and the like generate a large amount of gas when they come in contact with zinc powder in an alkaline liquid, and iron and nickel are not converted into mercury. And discloses an improved technology using lead as the current collector.
【０００４】特開昭６１−１１６７５５では使用する亜
鉛粉末（原料が電気亜鉛の場合の不純物含有量はＦｅ：
５〜２０ppm 、Ｃｄ：１〜５ppm 、Ｃｕ：１〜１０ppm
、Ｎｉ：１〜５ppm 、Ｃｏ：０．１〜１ppm 、Ａｇ：
１〜５ppm 等；原料が蒸留（常圧蒸留）亜鉛の場合の亜
鉛粉末の不純物含有量はＦｅ：１００〜３００ppm 、Ｃ
ｄ：５０〜１０００ppm 、Ｃｕ：１０〜１００ppm 、Ｎ
ｉ：１〜３０ppm 、Ｃｏ：１〜１０ppm 、Ａｇ：１〜１
０ppm 等）を単独で陰極活物質として用いた場合には、
電池が無負荷の状態でも該亜鉛粉末が電解質中で水素を
放出して電解質溶液に溶け込んでいく、いわゆる、自己
放電現象が生じ、電池の寿命を著しく減じてしまうこと
から鉄、カドミウム、銅、ニッケル、コバルトおよび銀
の含有量合計を９ppm 以下と特定することで電池特性を
改良している。Japanese Patent Application Laid-Open No. 61-116755 discloses zinc powder (impurity content when the raw material is electric zinc is Fe:
5-20 ppm, Cd: 1-5 ppm, Cu: 1-10 ppm
, Ni: 1 to 5 ppm, Co: 0.1 to 1 ppm, Ag:
When the raw material is distilled (normal pressure distilled) zinc, the impurity content of the zinc powder is Fe: 100 to 300 ppm, C
d: 50 to 1000 ppm, Cu: 10 to 100 ppm, N
i: 1 to 30 ppm, Co: 1 to 10 ppm, Ag: 1 to 1
0 ppm etc.) alone as the cathode active material,
Even when the battery is not loaded, the zinc powder releases hydrogen in the electrolyte and dissolves in the electrolyte solution, a so-called self-discharge phenomenon occurs, which significantly reduces the life of the battery, so that iron, cadmium, copper, The battery characteristics are improved by specifying the total content of nickel, cobalt and silver as 9 ppm or less.
【０００５】さらに特開平３−５６６３７では「亜鉛に
含まれる不純物は、亜鉛の腐食を促進し、亜鉛の純度が
９９．９９５％を下回るとき、特に不純物のＮｉ、Ｃ
ｒ、Ｍｏ、ＳｎおよびＳｂがそれぞれ１重量ppm を超え
るとき、あるいはＦｅが１０ppm を超えるときは、水素
ガス発生量は、影響が無視できない程に増加し、またば
らつきの原因にもなる」として不純物のそれぞれが１pp
m 以下でかつＦｅが１０ppm 以下であって、９９．９９
５以上の高純度亜鉛にＧａなどの特定の添加合金成分を
含有させて耐食性を向上させる改良技術を開示してい
る。特開平３−１５２８７０には「通常アルカリ電池用
亜鉛合金粉末の原料亜鉛中には鉄が１〜３ppm 含有され
ているが、メタル鉄の状態で亜鉛中に固有している場合
は亜鉛の耐食性には何等影響を与えるものではなく、し
かもこのメタル粉が１〜３ppm 中の大部分を占め、残り
のppb オーダーで鉄酸化物が存在しているものと考えら
れる。」とし純度９９．９９７％以上の亜鉛を溶融し、
これに合金元素を添加した溶融亜鉛合金を耐熱フィルタ
ーで濾過して亜鉛中に混在する鉄酸化物を除去する技術
を開示している。Japanese Unexamined Patent Publication (Kokai) No. 3-56637 discloses that "impurities contained in zinc promote the corrosion of zinc, and when the purity of zinc is less than 99.995%, particularly when the impurities are Ni and C
When each of r, Mo, Sn, and Sb exceeds 1 ppm by weight, or when Fe exceeds 10 ppm, the amount of hydrogen gas generated increases to such an extent that the effect cannot be ignored and also causes variation. " Each is 1pp
m and 10 ppm or less of Fe and 99.99
An improved technique for improving corrosion resistance by including a specific additive alloy component such as Ga in high purity zinc of 5 or more is disclosed. Japanese Patent Application Laid-Open No. 3-152870 discloses that "usually, zinc is contained in raw material zinc of an alkaline battery zinc alloy in an amount of 1 to 3 ppm. Does not have any effect, and it is considered that this metal powder occupies most of 1-3 ppm, and iron oxide is present in the remaining ppb order. " Melts the zinc
A technique is disclosed in which a molten zinc alloy to which an alloy element is added is filtered through a heat-resistant filter to remove iron oxide mixed in zinc.
【０００６】さらに特開平５−１６６５０７では亜鉛中
の随伴不純物として鉄の含有量を１ppm 以下とし、かつ
特定の添加元素を含有させて電池の耐洩液性を向上させ
たアルカリ電池用亜鉛合金粉末を開示している。Further, JP-A-5-166507 discloses a zinc alloy powder for an alkaline battery having an iron content of 1 ppm or less as an incidental impurity in zinc and containing a specific additive element to improve the leakage resistance of the battery. Is disclosed.
【０００７】すなわち電池用亜鉛合金粉末の改良技術
は、原料として使用する亜鉛の製造上やむをえない随伴
不純物である特定不純物を極力低減させかつ限定して使
用すること、また製造工程中で使用する設備、器具・器
材からの微量不純物混入を防止すること、随伴あるいは
混入した不純物を工程の中で取り除くこと等、にある。That is, the technology for improving zinc alloy powder for batteries is to minimize and limit the use of specific impurities, which are unavoidable accompanying the production of zinc used as a raw material, and to use equipment used in the production process. The purpose is to prevent trace impurities from being mixed in from instruments and equipment, and to remove accompanying or mixed impurities in the process.
【０００８】添加合金成分による電池特性の改良技術は
多数あり、近年環境問題からＨｇ、Ｐｂ、Ｃｄ等は少な
くする傾向にあるがその他の金属の添加効果については
各種の金属種について検討されている。例えばＡｌ、Ｉ
ｎ、Ｂｉ、Ｃａ、Ｍｇ、Ｓｂ等を用いこれらから選択さ
れ、かつ成分量の適量値を実験的に確認して最適組み合
わせを選択することで電池特性を向上させてきた。There are a number of techniques for improving battery characteristics by using added alloy components. In recent years, Hg, Pb, Cd, and the like have tended to be reduced due to environmental problems, but the effects of adding other metals have been studied for various metal types. . For example, Al, I
The battery characteristics have been improved by using n, Bi, Ca, Mg, Sb and the like, and selecting the optimum combination by experimentally confirming the appropriate values of the component amounts.
【０００９】また粉の形状、粒度分布、表面状態等を含
めた性状、物理特性の改良等による電池特性の改善につ
いても、例えば特開平４−２８４３５９では嵩比重を特
定した技術が、また特開平５−２９９０８７では真比重
を特定した改良技術がそれぞれ開示されている。Regarding the improvement of the battery characteristics by improving the properties and physical characteristics including the powder shape, particle size distribution, surface condition, etc., for example, Japanese Patent Application Laid-Open No. 4-284359 discloses a technique in which the bulk specific gravity is specified. Japanese Patent Application Laid-Open No. H5-299087 discloses an improved technique that specifies the true specific gravity.
【００１０】[0010]
【発明が解決しようとする課題】しかしながら従来の技
術にあっては、特定の不純物含有量を規制したり添加金
属を特定するだけでは不十分であり、特に亜鉛の純度が
極めて高いものを用いることや、また工程中で不純物の
混入を防止あるいは除去する措置を講ずることは、工程
管理の手間や設備が増え不良品の発生を増大させ製造コ
ストの上昇の原因ともなりかねない。However, in the prior art, it is not enough to regulate the specific impurity content or to specify the added metal. In particular, it is necessary to use one having extremely high zinc purity. In addition, taking measures to prevent or remove impurities from being mixed in the process may lead to an increase in troublesome processes and equipment, an increase in the number of defective products, and an increase in manufacturing costs.
【００１１】つまり特定の不純物を低減することで電池
特性は向上するがコスト増になること、また添加する合
金元素についてもその組み合わせおよび添加量の最適組
み合わせは無数にあるため現在までは技術的に十分満足
される亜鉛粉はできていない。In other words, by reducing specific impurities, the battery characteristics are improved, but the cost is increased. In addition, there are countless combinations of the alloying elements to be added and the optimum combination of the amounts of the alloying elements. No satisfactory zinc powder has been made.
【００１２】したがって、本発明の目的は随伴する特定
不純物を特別に低減させた亜鉛合金粉を用いることな
く、電池寿命に影響する自己放電による水素ガス発生を
大幅に抑制するアルカリ電池用亜鉛合金粉末およびその
製造方法を提供することにある。Accordingly, an object of the present invention is to provide a zinc alloy powder for an alkaline battery which greatly suppresses the generation of hydrogen gas due to self-discharge which affects the battery life without using a zinc alloy powder in which accompanying specific impurities are particularly reduced. And a method for manufacturing the same.
【００１３】[0013]
【課題を解決するための手段】従来不純物としての鉄の
含有量を極力下げることに努力が払われ、技術的に可能
になってきたが前述のように種々問題が生じているの
で、本発明者らはこの鉄の影響を少なくする手段を鋭意
検討した結果、Ａｌ、Ｉｎ、Ｂｉの所定量を選択し、さ
らにこの成分で合金化する際、Ａｌを最初とし、次いで
ＩｎもしくはＢｉの順に溶解することにより電池とした
場合鉄の影響が低減されることを見いだし本発明に到達
した。In the past, efforts have been made to reduce the content of iron as an impurity to the utmost, and this has become technically possible. However, since various problems have occurred as described above, the present invention As a result of intensive studies on means for reducing the influence of iron, the inventors selected a predetermined amount of Al, In, and Bi, and when alloying with this component, Al was first, then dissolved in order of In or Bi. As a result, the present inventors have found that the effect of iron is reduced when the battery is used, and arrived at the present invention.
【００１４】すなわち合金成分をこの順位で溶解すると
亜鉛粉の不純物として定量される鉄の含有量が０．００
０１重量％を超え、０．００１重量％以下であれば、電
池の負極活物質とした場合その特性は良好な状態を維持
する。本発明の電池用亜鉛合金粉末は上記鉄含有量にさ
らに添加合金元素としてＡｌ、Ｉｎ、Ｂｉで構成され、
詳しくはＡｌ０．００１〜０．０１重量％、Ｉｎ０．０
１〜０．０７重量％、Ｂｉ０．００１〜０．０２重量％
であり、これら成分範囲を逸脱したり、単独で含有させ
てもその効果は得られない。That is, when the alloy components are dissolved in this order, the iron content, which is determined as an impurity of the zinc powder, becomes 0.00
When the content is more than 01% by weight and 0.001% by weight or less, when the negative electrode active material of a battery is used, its characteristics are maintained in a good state. The zinc alloy powder for a battery of the present invention is composed of Al, In, and Bi as additional alloy elements in addition to the iron content,
More specifically, Al 0.001 to 0.01% by weight, In 0.0
1 to 0.07% by weight, Bi 0.001 to 0.02% by weight
However, the effect cannot be obtained even if the content is out of the range of these components or contained alone.
【００１５】以上要するに、不純物としての鉄の含有量
が０．０００１重量％を超え０．００１重量％以下であ
り、これに特定元素を加え、かつ添加合金元素の溶解順
を特定することで、これら相乗効果によって前記目的が
達成される。In short, the content of iron as an impurity is more than 0.0001% by weight and not more than 0.001% by weight. By adding a specific element to this and specifying the dissolution order of the added alloy element, The object is achieved by these synergistic effects.
【００１６】 したがって本発明は、精製した溶融亜鉛
を少量の添加金属で合金化した溶湯をアトマイズ法で噴
霧して粉体とした後、ふるい分けして亜鉛合金粉末とす
るアルカリ電池用亜鉛合金粉末の製造方法において、上
記合金化の際、Ａｌを最初に溶解し、次にＩｎもしくは
Ｂｉの順に溶解し、これら合金成分がＡｌ ０．００１
〜０．０１重量％、Ｉｎ ０．０１〜０．０７重量％お
よびＢｉ ０．００１〜０．０２重量％であり、かつＦ
ｅを０．０００１重量％を超え０．００１重量％以下含
有する亜鉛合金粉末を負極活物質とすることを特徴とす
るアルカリ電池用亜鉛合金粉末の製造方法を提供するも
のである。Accordingly, the present invention provides a method for producing a zinc alloy powder for an alkaline battery, which is obtained by spraying a molten metal obtained by alloying purified molten zinc with a small amount of an additional metal by an atomizing method and then sieving the zinc alloy powder. In the manufacturing method, at the time of the above alloying, Al is first dissolved, and then In or Bi is dissolved in this order.
-0.01 wt%, In 0.01-0.07 wt% and Bi 0.001-0.02 wt%, and F
The present invention provides a method for producing a zinc alloy powder for an alkaline battery, characterized in that a zinc alloy powder containing more than 0.0001% by weight and less than 0.001% by weight of e is used as a negative electrode active material.
【００１７】[0017]
【作用】前述のように本発明では通常使用される工業用
精製亜鉛を原料とすることができる。すなわちＦｅの含
有量は特に制限されることはないが０．００１重量％以
下であれはよい。このような亜鉛を溶解し、次にＡｌ、
Ｉｎ、Ｂｉの合金成分を添加して亜鉛合金とする。As described above, in the present invention, industrially used purified zinc which is usually used can be used as a raw material. That is, the Fe content is not particularly limited, but may be 0.001% by weight or less. Dissolve such zinc, then Al,
An alloy component of In and Bi is added to form a zinc alloy.
【００１８】Ａｌは亜鉛に合金化することにより合金粉
末粒子の表面を平滑化する効果があって反応性に関係す
る表面積を減少させガス発生を抑制する効果がある。Ｉ
ｎは合金粉末表面の水素過電圧を高めて電池として保存
中の腐食によるガス発生を抑制する作用があり、Ｂｉは
同様に放電前のガス発生を抑制する効果があるが放電後
のガス発生を増大する傾向がある。Al has an effect of smoothing the surface of the alloy powder particles by alloying with zinc, and has an effect of reducing a surface area related to reactivity and suppressing gas generation. I
n has the effect of increasing the hydrogen overvoltage on the surface of the alloy powder to suppress gas generation due to corrosion during storage as a battery, and Bi has the effect of suppressing gas generation before discharge, but increases gas generation after discharge. Tend to.
【００１９】上記合金化に際しては、Ａｌを最初にし、
ＩｎもしくはＢｉの順に溶解する必要がある。この溶解
の順位を違えてＡｌを後にすると、それを用いた電池特
性が悪くなる。In the above alloying, Al is used first,
It is necessary to dissolve in the order of In or Bi. If the order of dissolution is changed and Al is left behind, the battery characteristics using Al will deteriorate.
【００２０】この理由はＡｌを亜鉛に添加溶解するとＡ
ｌが酸化しやすいことにより脱酸素剤としても作用し、
それ自身一部酸化して形成した比重の軽いドロスが溶解
した亜鉛の上に浮上する。このＡｌ添加による合金化を
最初に行う際、亜鉛中に溶解しているかもしくは亜鉛中
に混在する微量の鉄や鉄の酸化物は一部はドロスと共に
浮上するがほとんどが亜鉛に溶解する。The reason is that when Al is added to and dissolved in zinc, A
Because l is easily oxidized, it also acts as a deoxidizer,
Light dross, which is partially oxidized and forms itself, floats on the dissolved zinc. When alloying by adding Al for the first time, a small amount of iron or iron oxide dissolved in zinc or mixed in zinc partially floats with dross, but is mostly dissolved in zinc.
【００２１】このメカニズムについては、微量の鉄がそ
のまま溶解し、微量の鉄はそのまま溶解し微量の鉄酸化
物は一部還元されることで金属鉄となり亜鉛中に溶解す
ることによると推定されるが明確ではない。その後でＩ
ｎもしくはＢｉが添加される。ＢｉやＩｎは亜鉛に溶解
して酸化剤もしくは還元剤として作用することがなく、
どちらを先に溶解しても良い。This mechanism is presumed to be due to the fact that a small amount of iron is dissolved as it is, a small amount of iron is dissolved as it is, and a small amount of iron oxide is partially reduced to metallic iron and dissolved in zinc. Is not clear. Then I
n or Bi is added. Bi and In do not dissolve in zinc and act as oxidizing or reducing agents,
Either one may be dissolved first.
【００２２】これら合金元素を添加した亜鉛合金溶湯を
得て引き続き通常のアトマイズを行うことにより亜鉛合
金粉末を得ることができる。By obtaining a zinc alloy melt to which these alloy elements are added and then performing normal atomization, a zinc alloy powder can be obtained.
【００２３】[0023]
【実施例１〜１８】図１は放電前のガス発生速度を求め
るため実施例および比較例に用いたガス発生量測定装置
の側断面図であって、この図を参照して以下説明する。Embodiments 1 to 18 FIG. 1 is a side sectional view of a gas generation amount measuring apparatus used in an embodiment and a comparative example for obtaining a gas generation speed before electric discharge, which will be described below with reference to FIG.
【００２４】通常の純度９９．９９５％以上であり、不
純物であるＦｅの含有量が０．０００１〜０．００１％
の範囲である亜鉛原料を約５００℃で溶解し、これに表
１に示す各元素の所定量を所定順に添加して亜鉛合金溶
湯を作成した。次に通常のアトマイズ法により高圧ガス
を噴射して亜鉛合金粉を作成し、これをふるい分けして
亜鉛合金粉末を得た。得られた亜鉛合金粉末についてＦ
ｅの含有量およびガス発生速度を求めた。The purity is usually 99.995% or more, and the content of Fe as an impurity is 0.0001 to 0.001%.
Was melted at about 500 ° C., and a predetermined amount of each element shown in Table 1 was added thereto in a predetermined order to prepare a molten zinc alloy. Next, a high pressure gas was injected by a normal atomizing method to prepare a zinc alloy powder, which was sieved to obtain a zinc alloy powder. About the obtained zinc alloy powder, F
e content and gas generation rate were determined.
【００２５】ここでガス発生速度については図１に示し
た測定装置により行った。すなわち、亜鉛合金粉末１を
所定量投入し、酸化亜鉛を飽和させた４０％ＫＯＨ溶液
２を添加後、流動パラフィン３を満たしてシリコーンゴ
ム栓４で封じた試験管５を６０℃の恒温槽６に保持し、
ガス発生速度をピペット７の目盛りで読んで求めた。Here, the gas generation rate was measured by the measuring device shown in FIG. That is, a predetermined amount of zinc alloy powder 1 is charged, a 40% KOH solution 2 saturated with zinc oxide is added, and then a test tube 5 filled with liquid paraffin 3 and sealed with a silicone rubber stopper 4 is placed in a thermostat bath 60 ° C. Hold on to
The gas generation rate was determined by reading on the scale of the pipette 7.
【００２６】表１に示されているように鉄の含有量は
０．０００１％から０．００１％程度であってしかも特
定の組成を有し、さらにＡｌを最初に加えて亜鉛合金粉
末とした実施例１〜１８ではいずれもガス発生量が許容
限度である約３０μl/g・day よりも少ない。As shown in Table 1, the iron content is about 0.0001% to 0.001% and has a specific composition, and Al is added first to form a zinc alloy powder. In all of Examples 1 to 18, the gas generation amount is smaller than the allowable limit of about 30 μl / g · day.
【００２７】[0027]
【比較例１〜１８】前記実施例に対し、合金成分を添加
することなく鉄の含有量のみ変化させた比較例１〜３で
はいずれもガス発生量が許容限度を上回っている。比較
例４〜１２はＡｌ、Ｂｉ、Ｉｎの単独添加あるいはこれ
らから選んだ２成分を添加したものであるが、Ｆｅの含
有量が０．０００１％から０．００１％のものであって
さらにＡｌを最初に添加したものであっても、そのガス
発生量は許容限度を上回っている。Comparative Examples 1 to 18 In Comparative Examples 1 to 3, in which only the iron content was changed without adding any alloying component, the gas generation amount exceeded the allowable limit. Comparative Examples 4 to 12 are those in which Al, Bi, and In are added alone or two components selected from them are added, but the content of Fe is 0.0001% to 0.001%, and Even if was added first, the amount of generated gas was above the allowable limit.
【００２８】比較例１３〜１４はいずれも添加成分のＢ
ｉが範囲外のものであるが、Ｆｅの含有量、添加順位が
所定の範囲あるいは順位であってもガス発生量は許容限
度を上回わり、また比較例１５〜１７は添加成分の投入
順位についてＡｌを後にしたものであり、いずれもガス
発生量は許容限度を上回っている。比較例１８はＦｅの
含有量が１０ppm を超えたものでありガス発生量が許容
限度に達する値になっている。In Comparative Examples 13 and 14, the additive component B
Although i is out of the range, even when the Fe content and the order of addition are within a predetermined range or order, the gas generation amount exceeds the allowable limit, and Comparative Examples 15 to 17 show the order of addition of the added components. In each case, the amount of gas generated exceeds the allowable limit. In Comparative Example 18, the Fe content exceeded 10 ppm, and the gas generation amount reached a value that reached an allowable limit.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】以上説明したように、本発明の方法によ
れば、亜鉛粉の代表的な不純物である鉄の含有量をppm
オーダーまで特別に低減することなく、特定の範囲
（０．０００１〜０．００１重量％）とし、さらに特定
の添加合金成分Ａｌ、ＩｎおよびＢｉを含有すると共
に、これら合金成分の溶解順位を特定して溶解しアトマ
イズするので、水素ガスの発生を抑制して電池特性を向
上させ得るアルカリ電池用亜鉛粉末が容易に得られる。As described above, according to the method of the present invention, the content of iron, which is a typical impurity of zinc powder, is reduced to ppm.
Without special reduction to the order, the specific range (0.0001 to 0.001% by weight), and further contain specific additive alloy components Al, In, and Bi, and the melting order of these alloy components is specified. As a result, the zinc powder for an alkaline battery which can suppress the generation of hydrogen gas and improve the battery characteristics can be easily obtained.
【図１】放電前のガス発生速度を求めるため実施例およ
び比較例に用いたガス発生量測定装置の側断面図であ
る。FIG. 1 is a side sectional view of a gas generation amount measuring apparatus used in Examples and Comparative Examples to determine a gas generation rate before discharge.
１ 亜鉛合金粉末 ２ ４０％ＫＯＨ溶液 ３ 流動パラフィン ４ シリコーンゴム栓 ５ 試験管 ６ 恒温槽 ７ ピペット Reference Signs List 1 zinc alloy powder 2 40% KOH solution 3 liquid paraffin 4 silicone rubber stopper 5 test tube 6 constant temperature bath 7 pipette
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−299082（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/42 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-299082 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/42
Claims (1)
金化した溶湯をアトマイズ法で噴霧して粉体とした後、
ふるい分けして亜鉛合金粉末とするアルカリ電池用亜鉛
合金粉末の製造方法において、上記合金化の際、Ａｌを
最初に溶解し、次にＩｎもしくはＢｉの順に溶解し、こ
れら合金成分がＡｌ ０．００１〜０．０１重量％、Ｉ
ｎ ０．０１〜０．０７重量％およびＢｉ ０．００１〜
０．０２重量％であり、かつＦｅを０．０００１重量％
を超え０．００１重量％以下含有する亜鉛合金粉末を負
極活物質とすることを特徴とするアルカリ電池用亜鉛合
金粉末の製造方法。A molten metal obtained by alloying purified molten zinc with a small amount of additional metal is atomized by atomization to obtain powder.
In the method for producing a zinc alloy powder for an alkaline battery which is sieved to obtain a zinc alloy powder, in the above alloying, Al is first dissolved, and then In or Bi is dissolved in this order. ~ 0.01% by weight, I
n 0.01-0.07% by weight and Bi 0.001-
0.02 % by weight and 0.0001% by weight of Fe
A method for producing a zinc alloy powder for an alkaline battery, comprising using a zinc alloy powder containing more than 0.001% by weight as the negative electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14130295A JP3343803B2 (en) | 1995-05-16 | 1995-05-16 | Zinc alloy powder for alkaline battery and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14130295A JP3343803B2 (en) | 1995-05-16 | 1995-05-16 | Zinc alloy powder for alkaline battery and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002198788A Division JP3997292B2 (en) | 2002-07-08 | 2002-07-08 | Zinc alloy powder for alkaline batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08315816A JPH08315816A (en) | 1996-11-29 |
| JP3343803B2 true JP3343803B2 (en) | 2002-11-11 |
Family
ID=15288732
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP3343803B2 (en) |
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| Publication number | Publication date |
|---|---|
| JPH08315816A (en) | 1996-11-29 |
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