JP3561299B2 - Zinc alloy powder for alkaline batteries - Google Patents
Zinc alloy powder for alkaline batteries Download PDFInfo
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- JP3561299B2 JP3561299B2 JP24058194A JP24058194A JP3561299B2 JP 3561299 B2 JP3561299 B2 JP 3561299B2 JP 24058194 A JP24058194 A JP 24058194A JP 24058194 A JP24058194 A JP 24058194A JP 3561299 B2 JP3561299 B2 JP 3561299B2
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- Prior art keywords
- alloy powder
- zinc alloy
- surface area
- repose
- specific surface
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- 239000000843 powder Substances 0.000 title claims description 33
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 30
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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】
【産業上の利用分野】
本発明はアルカリ電池用亜鉛合金粉末に関し、詳しくは粉末の安息角、比表面積を所定の範囲の値とし特定の元素を含有することにより、水素ガス発生、特に放電後のガス発生を抑制し、電池の耐漏液性を向上させたアルカリ電池用亜鉛合金粉末に関する。
【０００２】
【従来の技術】
電解液が苛性カリ、苛性ソーダのようなアルカリ水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概ね次のように製造されている。すなわち４Ｎ（純度９９．９９％）以上の高純度電気亜鉛を用いて少量の添加金属で合金化し、これをアトマイズ法で噴霧して得た不規則形状の粒子である。
【０００３】
このようなアルカリ電池用亜鉛合金粉末はアルカリ電解液中での水素過電圧が低く、電池内で放電された場合の化学分極も比較的大きいことから、水素過電圧を高め電解液による腐食を抑制するため水銀を添加した汞化亜鉛合金粉末が用いられてきた。
【０００４】
近年水銀による環境汚染が問題となり水銀含有量が０％すなわち無汞化亜鉛合金粉末を使用した電池の開発が期待されるようになった。今日例えばインジウムなどの亜鉛合金粉末添加元素を種々組み合わせたり、表面処理をする等で水銀含有量を０％とした無汞化亜鉛粉末が活物質として用いられるようになってきている。
【０００５】
【発明が解決しようとする課題】
しかしながら、無汞化亜鉛合金粉末を使用することで汞化亜鉛電池粉に求められていた特性を必ずしも満足するにはいたっておらず、例えば負極用亜鉛合金粉末のアルカリ電解液中での腐食による放電前後の水素ガス発生特性が十分でなく、特に過放電後のガス発生が多い点で問題があった。
【０００６】
したがって本発明は、このような問題点を解決するためのもので、亜鉛合金粉末の物理特性および合金組成を改良することにより、従来技術のものに比して水素ガス発生を抑制する、特に過放電後の水素ガス発生を抑制する無水銀アルカリ電池用亜鉛合金粉末を提供することを目的とするものである。
【０００７】
【課題を解決するための手段】
本発明者らは、この目的に沿って鋭意研究した結果、亜鉛合金粉末が特定の範囲の安息角と比表面積とを満足し、かつ特定の範囲の添加元素を有していると、これらの相乗効果によって特性が改善され、過放電後の水素ガス発生が大巾に抑制されることを見いだし本発明に到達した。
【０００８】
すなわち本発明は、安息角が４０度以下および比表面積が０.０１３〜０.０３ｍ2／ｇであってさらに、アルミニウムならば０.００５重量％以下、インジウムならば０.０７重量％以下、ビスマスならば０.０１重量％以下という制限条件の下で、アルミニウム、インジウムおよびビスマスを含み、残部が亜鉛および不可避不純物からなることを特徴とするアルカリ電池用亜鉛合金粉末である。
【０００９】
【作用】
上記のように構成することにより以下のような作用がある。
【００１０】
ここで各添加元素の効果としては以下のように推定されている。インジウムは亜鉛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、アルミニウムは亜鉛に合金化することにより、亜鉛合金粉末粒子の表面を平滑化する効果があって、これによって反応性に関係する表面積を減少させることとなり、ガス発生抑制効果を発揮せしめる効果がある。またビスマスは亜鉛の水素過電圧を高めてガス発生を抑制する効果を有している。
【００１１】
しかし、各成分元素の含有量が上記範囲を逸脱した場合には、水素ガスの発生を抑制する効果が得られなかったり、実用的な放電性能が維持できないという問題が生じる。またこれらの成分のいずれかが欠けても上記した本発明の効果は得られない。
【００１２】
また本発明の亜鉛合金粉末は比表面積０．０１３から０．０３ｍ２／ｇの範囲であること、安息角が４０度以下にあることが必要である。その範囲を越えると初期の水素ガス発生を抑制する効果が得られない。
【００１３】
ここでいう比表面積とはいわゆるＢＥＴ法（気体吸着法）にて求めた値である。また安息角とは図２に示したように、水平においた直径Ｄ（ｍｍ）の皿２上に漏斗３から亜鉛合金粉末１を流し落とし、その高さＨ（ｍｍ）を求め以下の式を用いて求めた。φｒ＝ｔａｎ−１（２Ｈ／Ｄ）
【００１４】
ここで亜鉛合金粉末の比表面積が０．０１３ｍ２／ｇ未満でガス発生抑制効果が少なくなるのは、比表面積値が低くなると亜鉛合金粉末の粒子形状が球状に近くなったり、粒子全体が大きくなり反応性が悪くなって放電前のガス発生は少なくなるが、本発明の目的とする過放電後のガス発生については、放電により表面が露出しその露出面が新たに活性化されガス発生量が多くなることによると思われる。
【００１５】
また比表面積が０．０３ｍ２／ｇを越えたりあるいは安息角が４０度を超えるものは亜鉛合金粉末の粒子形状が針状に近くなり反応性が良くなりすぎるものと思われる。
【００１６】
以下実施例、比較例によって本発明を具体的に説明する。尚以下の「％」はすべて重量％を意味する。
【００１７】
【実施例１〜４】
純度９９．９９５％以上の溶融した金属亜鉛にインジウム０．０４〜０．０６％を加えて調整したベースメタルに各添加元素（アルミニウムとビスマス）を所定範囲の含有量となるように溶解する。次にこの溶解物をアトマイズ法により高圧ガスによって噴射し、粉体にして亜鉛合金粉末を得た。
【００１８】
このようにして作製した亜鉛合金粉末をふるい分けして、安息角４０度以下、あるいは比表面積が０．０１３〜０．０３ｍ２／ｇの範囲の産物を得て電池用亜鉛合金粉末とした。なお、ベースメタルの粉末で所定の安息角、比表面積をもつものも用意した。
【００１９】
得られた電池用亜鉛合金粉末について過放電後のガス発生速度、比表面積、安息角を求めた。
【００２０】
ここで過放電後のガス発生速度については図１に示した測定法により行った。すなわち、亜鉛合金粉末をゲル化後、ＬＲ６型セル４（単３アルカリ電池）に組み込み、２０℃１０Ωで４８時間放電後、４５℃の恒温槽１１において、キャップ５つきの集電棒６をはずし、流動パラフィン７を満たしシリコーンゴム栓８で封じた試験官９中でのガス発生速度をピペット１０の目盛で読んで求めた。その結果を安息角、比表面積とともに表１に示した。
【００２１】
【比較例１〜７】
実施例と同様にインジウム０．０５％を添加したベースメタルを調整後、添加元素が所定範囲内外の含有量となるように溶解して、実施例の要領に従い亜鉛合金粉末を得てから、ふるい分けして安息角が４０度を超え比表面積が所定範囲内外のサンプルを用意した。
【００２２】
これらのサンプルについて、実施例と同様に過放電後のガス発生速度、比表面積、安息角を求め、その結果を表１に示した。
【００２３】
【表１】
【００２４】逆に比較例１〜７はアルミニウム、インジウム、ビスマスの添加成分の単独もしくは２種以上の組み合わせ、比表面積、所定範囲外の安息角を変化させたものであり、これらの例では水素ガス発生を抑制する効果は認められない。
【００２５】
【発明の効果】
以上の説明のごとく特定の範囲の添加元素を加え、安息角、比表面積が特定の範囲の亜鉛粉末はアルカリ電池の負極活物質に用いることにより、過放電後の水素ガス発生を大幅に抑制する。
【図面の簡単な説明】
【図１】過放電後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過放電後ガス発生測定装置の側断面図である。
【図２】安息角測定装置を示す側面図である。
【符号の説明】
１ 亜鉛合金粉末
２ 皿
３ 漏斗
４ ＬＲ６セル
５ キャップ
６ 集電棒
７ 流動パラフィン
８ シリコーンゴム栓
９ 試験管
１０ ピペット
１１ 恒温槽
Ｄ 皿の直径
Ｈ 粉末の高さ
φｒ 安息角[0001]
[Industrial applications]
The present invention relates to a zinc alloy powder for an alkaline battery, in particular, by controlling the angle of repose of the powder, the specific surface area to a value within a predetermined range and containing a specific element, to suppress hydrogen gas generation, particularly gas generation after discharge, The present invention relates to a zinc alloy powder for an alkaline battery having improved leakage resistance of the battery.
[0002]
[Prior 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 aqueous alkaline solution such as caustic potash and caustic soda is generally manufactured as follows. That is, the particles are irregularly shaped particles obtained by alloying with a small amount of added metal using high-purity electrozinc having a purity of 4N (purity: 99.99%) or more and spraying the alloy by an atomizing method.
[0003]
Such zinc alloy powder for alkaline batteries has a low hydrogen overvoltage in an alkaline electrolyte and a relatively large chemical polarization when discharged in the battery, so that the hydrogen overvoltage is increased and corrosion by the electrolyte is suppressed. Mercurized zinc alloy powders with added mercury have been used.
[0004]
In recent years, environmental pollution by mercury has become a problem, and the development of batteries using a mercury-free zinc alloy powder having a mercury content of 0% has been expected. Today, for example, zinc-free mercury-free zinc powder having a mercury content of 0% is being used as an active material by variously combining elements added with zinc alloy powder such as indium or by performing surface treatment.
[0005]
[Problems to be solved by the invention]
However, the use of non-melonized zinc alloy powder has not always been able to satisfy the properties required for zinc-melted battery powder. For example, discharge due to corrosion of zinc alloy powder for a negative electrode in an alkaline electrolyte. There was a problem in that the hydrogen gas generation characteristics before and after were not sufficient, and in particular, there was much gas generation after overdischarge.
[0006]
Accordingly, the present invention is intended to solve such a problem, and suppresses the generation of hydrogen gas as compared with the prior art by improving the physical properties and alloy composition of the zinc alloy powder. An object of the present invention is to provide a zinc alloy powder for a mercury-free alkaline battery that suppresses generation of hydrogen gas after discharge.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies for this purpose and found that the zinc alloy powder satisfies a specific range of the angle of repose and specific surface area, and that the zinc alloy powder has a specific range of the additive element. The inventors have found that the characteristics are improved by the synergistic effect, and the generation of hydrogen gas after overdischarge is largely suppressed, and the present invention has been achieved.
[0008]
That is, the present invention provides an angle of repose of 40 degrees or less and a specific surface area of 0.013 to 0.03 m 2 / g. Further, aluminum is 0.005% by weight or less, indium is 0.07% by weight or less, A zinc alloy powder for an alkaline battery, which contains aluminum, indium and bismuth under the restriction condition of 0.01% by weight or less in the case of bismuth, with the balance being zinc and unavoidable impurities.
[0009]
[Action]
With the above configuration, the following operation is provided.
[0010]
Here, the effect of each additive element is estimated as follows. Indium has the effect of increasing the hydrogen overvoltage on the surface of zinc alloy powder and suppressing gas generation due to corrosion during storage as a battery, and the effect of aluminum alloying with zinc to smooth the surface of zinc alloy powder particles. As a result, the surface area related to the reactivity is reduced, which has the effect of exerting the gas generation suppressing effect. Bismuth has the effect of increasing the hydrogen overvoltage of zinc to suppress gas generation.
[0011]
However, when the content of each component element deviates from the above range, there arises a problem that the effect of suppressing the generation of hydrogen gas cannot be obtained and that practical discharge performance cannot be maintained. In addition, even if any of these components is missing, the above-described effects of the present invention cannot be obtained.
[0012]
The zinc alloy powder of the present invention needs to have a specific surface area of 0.013 to 0.03 m 2 / g and a repose angle of 40 degrees or less. If it exceeds the range, the effect of suppressing the initial generation of hydrogen gas cannot be obtained.
[0013]
Here, the specific surface area is a value obtained by a so-called BET method (gas adsorption method). Also, as shown in FIG. 2, the angle of repose is as shown in FIG. 2. A zinc alloy powder 1 is poured from a
[0014]
When the specific surface area of the zinc alloy powder is less than 0.013 m 2 / g, the gas generation suppressing effect is reduced because the particle shape of the zinc alloy powder becomes nearly spherical or the whole particle becomes large when the specific surface area is reduced. As a result, gas generation before overdischarge decreases due to poor reactivity.However, with regard to gas generation after overdischarge, which is the object of the present invention, the surface is exposed by discharge and the exposed surface is newly activated, and the amount of gas generated It seems to be due to the increase.
[0015]
If the specific surface area exceeds 0.03 m 2 / g or the angle of repose exceeds 40 degrees, the zinc alloy powder is considered to have a needle-like particle shape and the reactivity becomes too good.
[0016]
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, all the following "%" means weight%.
[0017]
[Examples 1 to 4]
Each of the additional elements (aluminum and bismuth) is dissolved in a predetermined range in a base metal prepared by adding 0.04 to 0.06% of indium to molten zinc metal having a purity of 99.995% or more. Next, this melt was sprayed with a high-pressure gas by an atomizing method to obtain a zinc alloy powder.
[0018]
The zinc alloy powder produced in this manner was sieved to obtain a product having a repose angle of 40 degrees or less or a specific surface area in the range of 0.013 to 0.03 m 2 / g, which was used as a zinc alloy powder for a battery. A base metal powder having a predetermined angle of repose and a specific surface area was also prepared.
[0019]
The gas generation rate, specific surface area and angle of repose after overdischarge of the obtained zinc alloy powder for batteries were determined.
[0020]
Here, the gas generation rate after overdischarge was measured by the measuring method shown in FIG. That is, after the zinc alloy powder was gelled, incorporated in an LR6 type cell 4 (AA alkaline battery), and discharged at 20 ° C. for 10 hours for 48 hours, the current collecting rod 6 with the
[0021]
[Comparative Examples 1 to 7]
After adjusting the base metal to which 0.05% of indium was added in the same manner as in the example, the added element was dissolved so as to have a content outside the predetermined range, and a zinc alloy powder was obtained according to the procedure of the example. Then, a sample having a repose angle exceeding 40 degrees and a specific surface area within a predetermined range was prepared.
[0022]
For these samples, the gas generation rate after overdischarge, the specific surface area, and the angle of repose were determined in the same manner as in the examples, and the results are shown in Table 1.
[0023]
[Table 1]
Conversely, Comparative Examples 1 to 7 are those in which aluminum, indium, and bismuth are added alone or in combination of two or more of them, the specific surface area, and the angle of repose outside the predetermined range are changed. No effect of suppressing gas generation is observed.
[0025]
【The invention's effect】
As described above, a specific range of the additive element is added, and the repose angle and specific surface area of the zinc powder in the specific range are used for the negative electrode active material of the alkaline battery, thereby significantly suppressing the generation of hydrogen gas after overdischarge. .
[Brief description of the drawings]
FIG. 1 is a side sectional view of a post-overdischarge gas generation measuring apparatus used in Examples and Comparative Examples to determine a gas generation rate after overdischarge.
FIG. 2 is a side view showing a repose angle measuring device.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058194A JP3561299B2 (en) | 1994-09-08 | 1994-09-08 | Zinc alloy powder for alkaline batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058194A JP3561299B2 (en) | 1994-09-08 | 1994-09-08 | Zinc alloy powder for alkaline batteries |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002198789A Division JP2003068295A (en) | 2002-07-08 | 2002-07-08 | Zinc alloy powder for use in alkali battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0878017A JPH0878017A (en) | 1996-03-22 |
| JP3561299B2 true JP3561299B2 (en) | 2004-09-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24058194A Expired - Fee Related JP3561299B2 (en) | 1994-09-08 | 1994-09-08 | Zinc alloy powder for alkaline batteries |
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| Country | Link |
|---|---|
| JP (1) | JP3561299B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533902B (en) * | 2008-03-10 | 2014-01-08 | 松下电器产业株式会社 | Gelled negative electrode and alkaline battery |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025552A (en) * | 2000-07-12 | 2002-01-25 | Fdk Corp | Negative electrode zinc group alloy fine particle for alkaline battery, and alkaline battery using this fine particle |
| JP4736345B2 (en) * | 2004-04-23 | 2011-07-27 | パナソニック株式会社 | Alkaline battery |
| JP4560129B1 (en) * | 2009-09-07 | 2010-10-13 | パナソニック株式会社 | Alkaline battery |
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1994
- 1994-09-08 JP JP24058194A patent/JP3561299B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533902B (en) * | 2008-03-10 | 2014-01-08 | 松下电器产业株式会社 | Gelled negative electrode and alkaline battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0878017A (en) | 1996-03-22 |
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