JPH0799692B2 - Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the same - Google Patents
Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the sameInfo
- Publication number
- JPH0799692B2 JPH0799692B2 JP1296523A JP29652389A JPH0799692B2 JP H0799692 B2 JPH0799692 B2 JP H0799692B2 JP 1296523 A JP1296523 A JP 1296523A JP 29652389 A JP29652389 A JP 29652389A JP H0799692 B2 JPH0799692 B2 JP H0799692B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- alloy
- secondary battery
- alkaline
- zinc 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.)
- Expired - Lifetime
Links
- 239000011701 zinc Substances 0.000 title claims description 41
- 229910052725 zinc Inorganic materials 0.000 title claims description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 40
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052733 gallium Inorganic materials 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 5
- 229910000846 In alloy Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 10
- 210000001787 dendrite Anatomy 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- -1 zincate ions Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、亜鉛を負極の主活物質とし、アルカリ水溶液
を電解液とする二次電池に関し、充放電時に亜鉛の樹枝
状結晶の析出を抑制し、充放電サイクル寿命にすぐれた
アルカリ亜鉛二次電池を提供するものである。TECHNICAL FIELD The present invention relates to a secondary battery using zinc as a main active material of a negative electrode and an alkaline aqueous solution as an electrolytic solution, which suppresses deposition of zinc dendrites during charge and discharge. The present invention provides an alkaline zinc secondary battery having excellent charge / discharge cycle life.
従来の技術 従来よりこの種のアルカリ亜鉛二次電池は、エネルギー
密度が高いので早くから実用化がはかられたが、亜鉛負
極の充放電による可逆性に乏しく充放電サイクル寿命が
短いという問題があった。2. Description of the Related Art Conventionally, this type of alkaline zinc secondary battery has been put into practical use for a long time because of its high energy density, but there is a problem that the reversibility due to charge and discharge of the zinc negative electrode is poor and the charge / discharge cycle life is short. It was
このような問題を解決するために、電極への添加剤、電
解液量の最適化、電池の構造など様々な技術を融合する
ことが試みられている。それらの技術の中で、金属亜鉛
粒子に水銀を添加すると亜鉛電極表面の樹枝状結晶の析
出を迎え、充放電サイクル寿命の向上を図れることが知
られている。In order to solve such a problem, it has been attempted to combine various techniques such as an additive to the electrode, optimization of the amount of electrolyte, and battery structure. Among these techniques, it is known that when mercury is added to metallic zinc particles, dendrites are precipitated on the surface of the zinc electrode and the charge / discharge cycle life can be improved.
しかしながら、近年の低公害化の社会的ニーズが高まる
中で、使用する水銀量をより低下させ、さらに水銀を使
用せずに上記の性能を確保しなければならない。However, with the recent increasing social needs for low pollution, the amount of mercury used must be further reduced, and the above performance must be ensured without using mercury.
発明が解決しようとする課題 アルカリ亜鉛二次電池の密閉化において、過充電時に正
極から発生する酸素ガスは、セパレータを通して負極に
到達させ、負極で吸収除去する必要がある。負極板表面
でガス吸収に行わせるためにはなるべく多く負極表面を
気相中に露出させなければならず、そのためにフリーの
電解液を少なくした液規制型としなければならない。一
方電解液を少なくすると、放電時に生成した亜鉛酸イオ
ンを負極近傍に保持することが困難となり、亜鉛の樹枝
状結晶の析出が起こりやすくなる。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In sealing an alkaline zinc secondary battery, it is necessary to allow oxygen gas generated from the positive electrode during overcharge to reach the negative electrode through a separator and be absorbed and removed by the negative electrode. In order to absorb gas on the surface of the negative electrode plate, the surface of the negative electrode must be exposed in the gas phase as much as possible, and therefore, a liquid-regulating type in which the amount of free electrolyte is reduced must be adopted. On the other hand, when the amount of the electrolytic solution is reduced, it becomes difficult to keep zincate ions generated at the time of discharge in the vicinity of the negative electrode, and zinc dendrites are likely to be deposited.
また、反応を均一にする役目を果たすと考えられる水銀
の低減によりいっそう亜鉛の樹枝状結晶の析出が顕著と
なり、サイクル寿命の低下につながる。Further, the reduction of mercury, which is thought to play a role of making the reaction uniform, makes the dendrites of zinc more prominent, leading to a reduction in cycle life.
本発明はこのような問題を解決するもので、無汞化ある
いは極低汞化亜鉛合金を用いたアルカリ亜鉛二次電池に
おいて、亜鉛合金をインジウム，ガリウムを含んだ低沸
点合金で被覆することにより亜鉛の樹枝状結晶の析出を
防ぎ、良好なサイクル寿命を有した電池を供給すること
を目的とする。The present invention solves such a problem, and in an alkaline zinc secondary battery using a smooth or extremely low-reduction zinc alloy, by coating the zinc alloy with a low boiling point alloy containing indium and gallium, It is an object of the present invention to prevent precipitation of zinc dendrites and to provide a battery having a good cycle life.
課題を解決するための手段 上記の問題を解決するために本発明は、負極の主活物質
として無汞化あるいは、水銀量500ppmまでの低汞化亜鉛
合金を有するアルカリ亜鉛電池において、前記低汞化亜
鉛合金を、ガリウム、インジウムからなり液体状態であ
る合金で被覆したものである。ここでの被覆は、アルカ
リ金属水酸化物の水溶液中に亜鉛合金とガリウム、イン
ジウムからなり液体状態である合金を添加し攪拌するこ
とによりなしうる。Means for Solving the Problems In order to solve the above problems, the present invention is an unreacted or main alkaline material as a main active material of the negative electrode, in an alkaline zinc battery having a low-reduction zinc alloy of up to 500 ppm of mercury, the low-reduction. A zinc oxide alloy is coated with an alloy in the liquid state made of gallium and indium. The coating here can be performed by adding a zinc alloy, an alloy consisting of gallium and indium in a liquid state to an aqueous solution of an alkali metal hydroxide and stirring the mixture.
作用 この構成により、亜鉛合金の表面に被覆されたガリウ
ム、インジウムからなり液体状態である合金の効果で亜
鉛の樹枝状結晶の析出を防ぎ良好なサイクル寿命を有し
た電池を供給することができる。Action With this configuration, it is possible to supply a battery having a good cycle life by preventing the deposition of zinc dendrites by the effect of the liquid alloy containing gallium and indium coated on the surface of the zinc alloy.
本発明で用いるガリウム、インジウムからなり液体状態
である合金の作用効果は現在のところ定かではないが、
下記のように推察される。The action and effect of the liquid state alloy composed of gallium and indium used in the present invention is not clear at present,
It is guessed as follows.
亜鉛をアルカリ電解液中で放電すると亜鉛粒子からの亜
鉛酸イオンの溶出や、亜鉛微粒子（固体状）の溶出によ
り粒子表面はあれてくる。このような状況下において充
電を行うと、亜鉛粒子表面があれているために均一な亜
鉛の析出反応は起こりにくく、亜鉛粒子表面の突出した
部分に電荷が集中しその部分にのみ亜鉛の析出反応が起
きる。これが亜鉛の樹枝状結晶の析出の原因の一つであ
り、サイクル寿命を劣化させる結果となる。When zinc is discharged in an alkaline electrolyte, zinc oxide ions are eluted from the zinc particles and zinc fine particles (solid state) are eluted, so that the particle surface is exposed. When the battery is charged under such conditions, the uniform zinc deposition reaction does not occur because the surface of the zinc particle is rough, and the electric charge concentrates on the protruding part of the zinc particle surface and the zinc deposition reaction occurs only on that part. Occurs. This is one of the causes of precipitation of zinc dendrites, which results in deterioration of cycle life.
亜鉛粒子をガリウム、インジウムからなり液体状態であ
る合金で被覆することにより、表面が液体状態になり亜
鉛粒子表面のあれを防ぎ、さらに固体状の亜鉛微粒子の
溶出も抑えることができる。このことにより、亜鉛表面
の反応がより均一になり、樹枝状結晶の析出を防ぎ、サ
イクル寿命の良好なアルカリ亜鉛二次電池を提供できる
こととなる。By coating the zinc particles with an alloy in the liquid state composed of gallium and indium, the surface is in a liquid state and the surface of the zinc particles can be prevented from being roughened, and elution of solid zinc fine particles can be suppressed. As a result, the reaction on the zinc surface becomes more uniform, the deposition of dendrites is prevented, and an alkaline zinc secondary battery having a good cycle life can be provided.
実施例 無汞化亜鉛合金粒子表面を、ガリウム、インジウムから
なり液体状態である合金で被覆した亜鉛合金粉（以下、
表面被覆亜鉛合金）の製造法と、その亜鉛合金粉をペー
スト式負極板とし、アルカリ亜鉛二次電池に適用した例
について説明する。Examples Zinc alloy powders obtained by coating the surface of unsolicited zinc alloy particles with an alloy in the liquid state made of gallium and indium (hereinafter,
A method for producing a surface-coated zinc alloy) and an example in which the zinc alloy powder is used as a paste type negative electrode plate and applied to an alkaline zinc secondary battery will be described.
第１図は、本実施例で得られた表面被覆亜鉛合金粉末の
粒子モデルを現した断面図である。第１図において、１
は亜鉛合金、２はインジウム、ガリウムからなり液体状
態である合金被膜である。FIG. 1 is a sectional view showing a particle model of the surface-coated zinc alloy powder obtained in this example. In FIG. 1, 1
Is a zinc alloy, 2 is an alloy coating composed of indium and gallium in a liquid state.
本実施例における表面被覆亜鉛合金は、以下のようにし
て作成した。すなわち、５重量％の水酸化カリウム水溶
液１中に無汞化亜鉛合金を2kg投入し、その後にイン
ジウム，ガリウム合金を適量添加して攪拌する。約１時
間アルカリ水溶液中で攪拌した後、蒸溜水を用いて10回
以上ろ過洗浄する。蒸溜水で洗浄した後アセトンで水分
を取り除き、60℃で乾燥させる。以上のような工程によ
り表面被覆亜鉛合金を得た。この合金が、第１図に示し
たように表面のインジウム、およびガリウムの濃度が高
くなっていることを確認するために、合金表面の簡易定
量分析を行った。得られた結果を表１に示した。The surface-coated zinc alloy in this example was prepared as follows. That is, 2 kg of the unstabilized zinc alloy is put into a 5 wt% potassium hydroxide aqueous solution 1, and thereafter, an appropriate amount of indium and gallium alloy is added and stirred. After stirring in an alkaline aqueous solution for about 1 hour, it is filtered and washed 10 times or more with distilled water. After washing with distilled water, remove water with acetone and dry at 60 ° C. The surface-coated zinc alloy was obtained by the above steps. In order to confirm that the concentration of indium and gallium on the surface of this alloy is high as shown in FIG. 1, simple quantitative analysis of the alloy surface was performed. The obtained results are shown in Table 1.
資料No.1は被覆する前の無汞化亜鉛合金を、No.2,No.3
およびNo.4は、それぞれガリウム，インジウム合金で、
0.2,0.5,および1.5重量％それぞれ被覆された合金であ
る。この分析結果から明らかなように、表面被覆合金に
おいて、ガリウム，インジウムが、被覆するために投入
した全体に対する割合よりも、表面の割合のほうが高く
なっている。つまり、上記の方法で作成することにより
得られた合金は、第１図に示したような表面被覆合金で
あることがわかった。また、アルカリ水溶液中で被覆す
るのではなくて、乾式で被覆した表面被覆合金について
も簡易定量分析を行った結果、同様の結果を得た。 Material No. 1 is a non-coated zinc alloy before coating, No. 2, No. 3
And No. 4 are gallium and indium alloys,
Alloys coated with 0.2, 0.5, and 1.5 wt% respectively. As is clear from this analysis result, in the surface coating alloy, the ratio of gallium and indium in the surface is higher than the ratio of gallium and indium to the total amount input for coating. That is, it was found that the alloy obtained by the above method was a surface coating alloy as shown in FIG. Further, similar results were obtained as a result of a simple quantitative analysis of the surface coating alloy which was not coated in the alkaline aqueous solution but was coated by the dry method.
第２図は、本実施例で用いた円筒型ニッケル亜鉛蓄電池
の構造断面図である。第２図において、３は本発明にお
いて得られた表面被覆亜鉛合金粉末と酸化亜鉛粉末を主
体とするペーストを銅のパンチングメタルに塗着したペ
ースト式負極板、４は多孔性焼結ニッケル基板の孔中
に、水酸化ニッケルを主体とする活物質を含浸させた焼
結式正極板、５は含液材とセパレータである。６は金属
ケース、７は（＋）のリード板、８は（−）のリード
板、９は絶縁チューブ、10は底部絶縁板、11は封口板、
12はキャップ、13は安全弁、14はガスケットである。FIG. 2 is a structural cross-sectional view of the cylindrical nickel-zinc storage battery used in this example. In FIG. 2, 3 is a paste type negative electrode plate in which a paste mainly composed of the surface-coated zinc alloy powder and the zinc oxide powder obtained in the present invention is applied to a copper punching metal, and 4 is a porous sintered nickel substrate. Sintered positive electrode plates 5 in which holes are impregnated with an active material mainly containing nickel hydroxide are a liquid-containing material and a separator. 6 is a metal case, 7 is a (+) lead plate, 8 is a (-) lead plate, 9 is an insulating tube, 10 is a bottom insulating plate, 11 is a sealing plate,
12 is a cap, 13 is a safety valve, and 14 is a gasket.
上述の構成により試作した電池において、充放電サイク
ル試験をおこなった。第３図に、0.1Cで一定時間（13時
間）充電し、1Cで放電したときの充放電サイクル数と、
放電容量の変化の関係を示した。第３図中（ａ）が本発
明による表面被覆亜鉛合金を用いた場合のサイクル特性
曲線であり、表１における資料No.3を用いたものであ
る。（ｂ）は資料No.1を用いたものである。図より明ら
かなようにインジウム，ガリウムからなり液体状態であ
る合金で被覆した亜鉛合金を用いた場合は、被覆してい
ないものに較べてサイクル数の進行にともなった容量の
減少が少ないことがわかる。A charging / discharging cycle test was performed on the battery prototyped with the above configuration. Fig. 3 shows the number of charge and discharge cycles when charging at 0.1C for a certain time (13 hours) and discharging at 1C,
The relationship of changes in discharge capacity is shown. In FIG. 3, (a) is a cycle characteristic curve in the case of using the surface-coated zinc alloy according to the present invention, using the data No. 3 in Table 1. (B) uses the material No.1. As can be seen from the figure, when the zinc alloy coated with the alloy in indium and gallium in the liquid state is used, the capacity decrease with the progress of the cycle number is smaller than that of the uncoated alloy. .
発明の効果 以上のように、本発明によれば、アルカリ亜鉛２次電池
において、亜鉛合金表面を、インジウム、ガリウムから
なり液体状態である合金で被覆することにより、亜鉛表
面の充放電反応を均一にし、亜鉛の樹脂状結晶の析出を
抑えてサイクル寿命の良好な電池を提供することができ
る。EFFECTS OF THE INVENTION As described above, according to the present invention, in the alkaline zinc secondary battery, by coating the zinc alloy surface with an alloy of indium and gallium in a liquid state, the charge and discharge reaction on the zinc surface is made uniform. In addition, it is possible to provide a battery having a good cycle life by suppressing the precipitation of resinous crystals of zinc.
第１図は本発明の実施例における表面被覆亜鉛合金粉末
の粒子モデルを現した断面図、第２図は表面被覆亜鉛合
金を用いたニッケル亜鉛蓄電池の断面図、第３図は充放
電サイクル数と放電電気量との関係を示す図である。 １……無汞化亜鉛合金、２……インジウム、ガリウムか
らなり液体状態である合金の被膜、３……負極板、４…
…正極板、５……含液剤とセパレータ。FIG. 1 is a sectional view showing a particle model of a surface-coated zinc alloy powder in an example of the present invention, FIG. 2 is a sectional view of a nickel-zinc storage battery using a surface-coated zinc alloy, and FIG. 3 is a charge / discharge cycle number. It is a figure which shows the relationship between discharge electric quantity. 1 ... Unprocessed zinc alloy, 2 ... Indium and gallium alloy coating in liquid state, 3 ... Negative electrode plate, 4 ...
... Positive electrode plate, 5 ... Liquid-containing agent and separator.
Claims (5)
量500ppmまでの低汞化亜鉛合金を有するアルカリ亜鉛二
次電池において、前記無汞化あるいは低汞化亜鉛合金
は、ガリウム、インジウムからなり液体状態である合金
により被覆されているアルカリ亜鉛二次電池用亜鉛合
金。1. An alkaline zinc secondary battery having a non-reducing or low-reducing zinc alloy having a mercury content of up to 500 ppm as a main active material of a negative electrode, wherein the non-reducing or low-reducing zinc alloy is selected from gallium and indium. A zinc alloy for an alkaline zinc secondary battery, which is coated with an alloy in the liquid state.
化亜鉛合金を、アルカリ金属水酸化物の水溶液中に添加
した後、ガリウム、インジウムからなり液体状態である
合金を添加し撹拌することにより亜鉛合金を被覆するこ
とを特徴とするアルカリ亜鉛二次電池用亜鉛の製造法。2. A non-blended or low-blended zinc alloy with a mercury content up to 500 ppm is added to an aqueous solution of an alkali metal hydroxide, and then an alloy consisting of gallium and indium in a liquid state is added and stirred. A method for producing zinc for an alkaline zinc secondary battery, which is characterized in that the zinc alloy is coated thereby.
化亜鉛合金に、ガリウム、インジウムからなり液体状態
である合金を添加し、乾式で撹拌することにより亜鉛合
金を被覆することを特徴とするアルカリ亜鉛二次電池用
亜鉛合金の製造法。3. A zinc alloy coated by adding dry an alloy of gallium and indium in a liquid state to a zinc-free alloy having a mercury content of up to 500 ppm, and coating the zinc alloy by dry stirring. And a method for producing a zinc alloy for an alkaline zinc secondary battery.
ム、水酸化ナトリウム、水酸化リチウム、水酸化ルビジ
ウム及び水酸化セシウムからなる群より選択したいずれ
かである特許請求の範囲第２項記載のアルカリ亜鉛二次
電池用亜鉛合金の製造法。4. The method according to claim 2, wherein the alkali metal hydroxide is any one selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide and cesium hydroxide. Manufacturing method of zinc alloy for alkaline zinc secondary battery.
化亜鉛合金を、ガリウム、インジウムからなり液体状態
である合金で被覆したアルカリ亜鉛二次電池用亜鉛合金
を負極活物質としたことを特徴とするアルカリ亜鉛二次
電池。5. A negative electrode active material comprising a zinc alloy for alkaline-zinc secondary batteries, which is a non-blended or low-blended zinc alloy having a mercury content of up to 500 ppm and coated with an alloy consisting of gallium and indium in a liquid state. An alkaline zinc secondary battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1296523A JPH0799692B2 (en) | 1989-11-15 | 1989-11-15 | Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1296523A JPH0799692B2 (en) | 1989-11-15 | 1989-11-15 | Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03156855A JPH03156855A (en) | 1991-07-04 |
| JPH0799692B2 true JPH0799692B2 (en) | 1995-10-25 |
Family
ID=17834636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1296523A Expired - Lifetime JPH0799692B2 (en) | 1989-11-15 | 1989-11-15 | Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0799692B2 (en) |
-
1989
- 1989-11-15 JP JP1296523A patent/JPH0799692B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03156855A (en) | 1991-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100449826C (en) | Zinc negative electrode secondary battery, zinc negative electrode of the battery and their preparation method | |
| US5122375A (en) | Zinc electrode for alkaline batteries | |
| JP2507161B2 (en) | Zinc alloy for zinc alkaline battery, method for producing the same, and zinc alkaline battery using the same | |
| JPH0799692B2 (en) | Zinc alloy for alkaline zinc secondary battery, method for producing the same, and alkaline zinc secondary battery using the same | |
| JPH06260166A (en) | Nickel electrode for alkaline storage battery | |
| JP3204275B2 (en) | Nickel electrode for alkaline storage battery | |
| JPH079806B2 (en) | Zinc electrode for alkaline storage battery | |
| JP2614486B2 (en) | Alkaline zinc storage battery | |
| JPH079807B2 (en) | Zinc electrode for alkaline storage battery | |
| JP2538303B2 (en) | Zinc electrode for alkaline storage battery | |
| JPH073793B2 (en) | Alkaline zinc storage battery | |
| JP2931316B2 (en) | Manufacturing method of alkaline zinc storage battery | |
| JPS58137964A (en) | Alkaline zinc storage battery | |
| JP2000106184A (en) | Nickel hydroxide electrode for alkaline storage battery, and the alkaline storage battery using this electrode | |
| JPS58137963A (en) | Alkaline zinc storage battery | |
| JPH09245827A (en) | Manufacturing method of alkaline storage battery | |
| JPH0690926B2 (en) | Alkaline zinc secondary battery | |
| JPH0765835A (en) | Alkali zinc storage battery | |
| JPH0576743B2 (en) | ||
| JPH02103858A (en) | Zinc pole and alkaline battery equipped with the zinc pole | |
| JPH10233210A (en) | Alkaline storage battery | |
| JPH071695B2 (en) | Alkaline zinc storage battery | |
| JPH0582022B2 (en) | ||
| JPH0584027B2 (en) | ||
| JPH0782846B2 (en) | Alkaline zinc storage battery |