JPH0773881A - Zinc oxide alloy powder for alkaline zinc storage battery and manufacture thereof - Google Patents
Zinc oxide alloy powder for alkaline zinc storage battery and manufacture thereofInfo
- Publication number
- JPH0773881A JPH0773881A JP6147006A JP14700694A JPH0773881A JP H0773881 A JPH0773881 A JP H0773881A JP 6147006 A JP6147006 A JP 6147006A JP 14700694 A JP14700694 A JP 14700694A JP H0773881 A JPH0773881 A JP H0773881A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- alloy powder
- storage battery
- alkaline
- zinc oxide
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000843 powder Substances 0.000 title claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011701 zinc Substances 0.000 title claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 33
- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 32
- 238000003860 storage Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 24
- 239000002344 surface layer Substances 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910004866 Cd-Zn Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 zincate ions Chemical class 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルカリ亜鉛蓄電池用酸
化亜鉛合金粉末およびその製造方法、並びに該酸化亜鉛
合金粉末を負極活物質として用いたアルカリ亜鉛蓄電池
に関するものである。TECHNICAL FIELD The present invention relates to a zinc oxide alloy powder for an alkaline zinc storage battery, a method for producing the same, and an alkaline zinc storage battery using the zinc oxide alloy powder as a negative electrode active material.
【０００２】[0002]
【従来の技術】近年、電気自動車用電源等の種々の機器
において、電池の高エネルギー密度化、高性能化が図ら
れており、このような用途に用いられる電池としてアル
カリ亜鉛蓄電池がある。このアルカリ亜鉛蓄電池は、陽
極活物質にニッケル、銀等、負極活物質に亜鉛を用いる
ものである。2. Description of the Related Art In recent years, in various devices such as power sources for electric vehicles, higher energy density and higher performance of batteries have been attempted, and alkaline zinc storage batteries are used as batteries for such applications. This alkaline zinc storage battery uses nickel, silver or the like as the positive electrode active material and zinc as the negative electrode active material.
【０００３】このアルカリ亜鉛蓄電池の負極活物質とし
ての亜鉛は、単位重量当りのエネルギー密度が大きくし
かも安価であり、しかも無公害であるという利点を有す
る。Zinc as the negative electrode active material of this alkaline zinc storage battery has the advantages that it has a large energy density per unit weight, is inexpensive, and is pollution-free.
【０００４】しかるに、亜鉛を負極活物質とした場合、
次のような欠点があることが、特開平２−３００６２号
公報や特開平４−２８１６０号公報に記載されている。However, when zinc is used as the negative electrode active material,
The following drawbacks are described in Japanese Patent Laid-Open Nos. 2-30062 and 4-28160.
【０００５】すなわち、亜鉛からなる負極活物質が放電
過程あるいは充電過程において溶解析出または電析し、
シェイブチェンジやデンドライトショートの問題を引き
起こす。That is, a negative electrode active material made of zinc is dissolved and deposited or electrodeposited in a discharging process or a charging process,
Causes problems with shave changes and dendrite shorts.
【０００６】充電過程では、亜鉛酸イオンから析出され
る亜鉛金属結晶はデンドライト結晶になり易い。このた
め充放電を繰り返すことによる電池容量の低下、すなわ
ちサイクル特性が悪い。During the charging process, zinc metal crystals deposited from zincate ions tend to become dendrite crystals. For this reason, the battery capacity decreases due to repeated charging and discharging, that is, cycle characteristics are poor.
【０００７】このため、アルカリ亜鉛蓄電池の実用化の
ためにはシェイブチェンジおよびデンドライトショート
を減少させる必要があり、このためには電流分布の均一
化が必要であり、亜鉛極板の導電性向上がより一層に望
まれるとされている。Therefore, in order to put the alkaline zinc storage battery into practical use, it is necessary to reduce the shave change and dendrite short circuit. For this purpose, it is necessary to make the current distribution uniform and to improve the conductivity of the zinc electrode plate. It is said that it will be further desired.
【０００８】このような課題を解決するために種々の提
案がなされている。例えば、酸化亜鉛を金属亜鉛で被覆
したものを用いたり（特開平２−３００６２号公報）、
亜鉛合金を活物質として用いた例（特開平４−２８１６
０号公報）、種々の酸化物を添加した例（特公昭５１−
３２３６５号公報）がある。しかし、これらの提案にお
いても、依然として高エネルギー密度で、しかも長寿命
のアルカリ亜鉛蓄電池用負極活物質としては不充分であ
る。Various proposals have been made to solve such problems. For example, zinc oxide coated with metallic zinc may be used (Japanese Patent Laid-Open No. 2-30062).
Example using zinc alloy as active material (Japanese Patent Laid-Open No. 4-2816)
No. 0), examples of adding various oxides (Japanese Patent Publication No. 51-
32365). However, these proposals are still insufficient as a negative electrode active material for alkaline zinc storage batteries having a high energy density and a long life.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記従来の
課題に鑑みなされたものであり、デンドライトショート
等を生じることが少ない、少なくとも表面層が酸化され
た酸化亜鉛合金粉末およびその製造方法、並びに該合金
粉末を負極活物質として用いることによりサイクル特性
が大幅に改善されたアルカリ亜鉛蓄電池を提供すること
を目的とするものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is a zinc oxide alloy powder in which at least a surface layer is oxidized and which is less likely to cause dendrite shorts, and a method for producing the same. Another object of the present invention is to provide an alkaline zinc storage battery having significantly improved cycle characteristics by using the alloy powder as a negative electrode active material.
【００１０】[0010]
【課題を解決するための手段】本発明の上記目的は、次
に示す酸化亜鉛合金粉末を用いることによって達成され
る。The above object of the present invention can be achieved by using the zinc oxide alloy powder shown below.
【００１１】すなわち、本発明は、少なくとも表面層が
酸化されていることを特徴とするアルカリ亜鉛蓄電池用
酸化亜鉛合金粉末にある。That is, the present invention resides in a zinc oxide alloy powder for alkaline zinc storage batteries, characterized in that at least the surface layer is oxidized.
【００１２】ここでいう少なくとも表面層が酸化された
酸化亜鉛合金粉末とは、亜鉛合金粉末の少なくとも表面
層が酸化された状態のものであり、好ましくは金属元素
（亜鉛および添加元素）の５重量％以上酸化されたもの
であり、さらに好ましくは３０重量％以上酸化されたも
のである。The zinc oxide alloy powder in which at least the surface layer is oxidized is a state in which at least the surface layer of the zinc alloy powder is oxidized, and preferably 5 weight% of the metal element (zinc and additive element). % Or more, more preferably 30% by weight or more.
【００１３】また、この亜鉛合金粉末は、Ｃｄ、Ｐｂ、
Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂｉ、Ａｌから選ばれ
る少なくとも１種の元素と亜鉛および不可避不純物から
なることが望ましい。これらＣｄ、Ｐｂ等の添加元素の
含有割合は、酸化亜鉛合金粉末中、金属元素換算で、
０．１〜３０重量％であることが好ましく、さらに好ま
しくは１〜１０重量％である。Further, this zinc alloy powder contains Cd, Pb,
It is preferable that at least one element selected from Sn, In, Ga, Tl, Ca, Bi, and Al, zinc, and inevitable impurities are contained. The content ratios of these additional elements such as Cd and Pb are calculated in terms of metal elements in the zinc oxide alloy powder,
It is preferably 0.1 to 30% by weight, and more preferably 1 to 10% by weight.
【００１４】本発明の少なくとも表面層が酸化された亜
鉛合金粉末の好ましい製造方法としては、亜鉛合金粉末
を大気中で水酸化カリウム水溶液を用いて表面層を酸化
させることである。A preferred method for producing a zinc alloy powder having at least the surface layer thereof oxidized according to the present invention is to oxidize the surface layer of the zinc alloy powder using an aqueous potassium hydroxide solution in the atmosphere.
【００１５】この方法による亜鉛合金粉末の表面酸化
は、発熱を伴った急激な酸化反応が進行する。そこで、
反応時に、亜鉛合金粉末と接触する大気中の酸素量を制
限することにより、亜鉛合金粉末の表面層の酸化度を容
易に制御できる。In the surface oxidation of the zinc alloy powder by this method, a rapid oxidation reaction accompanied by heat generation proceeds. Therefore,
By limiting the amount of oxygen in the atmosphere that comes into contact with the zinc alloy powder during the reaction, the degree of oxidation of the surface layer of the zinc alloy powder can be easily controlled.
【００１６】この製造方法の詳細を示すフローチャート
を図１に示す。この図１においては、フタ付きガラス容
器の開閉によって亜鉛合金粉末と接触する大気中の酸素
量を制限している。A flow chart showing the details of this manufacturing method is shown in FIG. In FIG. 1, the amount of oxygen in the atmosphere in contact with the zinc alloy powder is limited by opening and closing the glass container with a lid.
【００１７】本発明では、この酸化亜鉛合金粉末をアル
カリ亜鉛蓄電池の負極活物質の少なくとも一部として用
いる。In the present invention, this zinc oxide alloy powder is used as at least a part of the negative electrode active material of the alkaline zinc storage battery.
【００１８】このような負極活物質は、好ましくは下記
の組み合わせ： （１）金属亜鉛粉末、 （２）Ｃｄ、Ｐｂ、Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂ
ｉ、Ａｌから選ばれる少なくとも１種の元素と亜鉛およ
び不可避不純物からなる亜鉛合金粉末、 （３）少なくとも表面層が酸化されてなり、Ｃｄ、Ｐ
ｂ、Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂｉ、Ａｌから選
ばれる少なくとも１種の元素と亜鉛および不可避不純物
からなる酸化亜鉛合金粉末、からなる。Such a negative electrode active material is preferably the following combination: (1) metallic zinc powder, (2) Cd, Pb, Sn, In, Ga, Tl, Ca, B.
Zinc alloy powder consisting of at least one element selected from i and Al, zinc and unavoidable impurities (3) At least the surface layer is oxidized to form Cd, P
It is composed of at least one element selected from b, Sn, In, Ga, Tl, Ca, Bi and Al, and a zinc oxide alloy powder containing zinc and inevitable impurities.
【００１９】このような、酸化亜鉛合金粉末を負極活物
質の少なくとも一部に用いることにより、デントライト
ショート等が生じることが少ない。それ故、この酸化亜
鉛合金粉末を負極活物質の少なくとも一部としてに配置
したアルカリ亜鉛蓄電池は、サイクル特性が大幅に向上
する。By using such a zinc oxide alloy powder as at least a part of the negative electrode active material, dentite short circuit or the like is less likely to occur. Therefore, the alkaline zinc storage battery in which the zinc oxide alloy powder is disposed as at least a part of the negative electrode active material has a significantly improved cycle characteristic.
【００２０】[0020]
【実施例】以下、実施例等に基づき本発明を具体的に説
明する。EXAMPLES The present invention will be specifically described below based on Examples and the like.
【００２１】実施例１ 純度９９．９９７％以上の亜鉛地金を約５５０℃で溶融
し、これに表１に示すごとく、金属亜鉛に対しカドミウ
ムの含有率５．０重量％となるように添加して亜鉛合金
を作製し、これを高圧アルゴンガス（噴出圧５ｋｇ／ｃ
ｍ2）を使って噴霧して粉体化した。 Example 1 Zinc metal having a purity of 99.997% or more was melted at about 550 ° C. and added to the metal zinc so that the content of cadmium was 5.0% by weight, as shown in Table 1. To produce a zinc alloy, which is then pressurized with high-pressure argon gas (spray pressure 5 kg / c
m 2 ) and atomized into powder.
【００２２】得られた５重量％Ｃｄ−Ｚｎ合金粉末の一
部を、プロパンガスバーナーで加熱酸化して少なくとも
表面層が酸化された酸化亜鉛合金粉末を作製した。得ら
れた酸化亜鉛合金粉末は、少なくとも表面層が酸化され
ていた。A part of the obtained 5 wt% Cd-Zn alloy powder was heated and oxidized by a propane gas burner to prepare a zinc oxide alloy powder in which at least the surface layer was oxidized. At least the surface layer of the obtained zinc oxide alloy powder was oxidized.
【００２３】負極活物質の調製として、粒径１〜５０μ
ｍの酸化亜鉛合金（５重量％Ｃｄ−Ｚｎ）粉末４０重量
部に対して、粒径０．１〜５ｍｍの金属亜鉛粉末を２０
重量部、粒径１〜５０μｍの亜鉛合金（５重量％Ｃｄ−
Ｚｎ）粉末を４０重量部加え混合した。As the preparation of the negative electrode active material, the particle size is 1 to 50 μm.
m zinc oxide alloy (5 wt% Cd-Zn) powder of 40 parts by weight, metal zinc powder having a particle diameter of 0.1 to 5 mm
Parts by weight, zinc alloy with a particle size of 1 to 50 μm (5 wt% Cd-
40 parts by weight of Zn) powder were added and mixed.
【００２４】次に、前記活物質９５重量％、フッ素樹脂
５重量％から成る混合粉末に水を加え混練し、ペースト
を得、導電体上に圧着して負極とした。このように作製
した負極と公知の焼結式ニッケル陽極とを組み合わせ
て、公称容量２Ａｈの密閉型ニッケル−亜鉛蓄電池を得
た。Next, water was added to a mixed powder composed of 95% by weight of the active material and 5% by weight of a fluororesin, and kneaded to obtain a paste, which was pressure-bonded onto a conductor to obtain a negative electrode. By combining the negative electrode thus produced and a known sintered nickel anode, a sealed nickel-zinc storage battery having a nominal capacity of 2 Ah was obtained.
【００２５】実施例２ 純度９９．９９７％以上の亜鉛地金を約５５０℃で溶融
し、これに表１に示すごとく、金属亜鉛に対しカドミウ
ムの含有率５．０重量％となるように添加して亜鉛合金
を作製し、これを実施例１と同様に噴霧して粉体化し
た。 Example 2 Zinc ingot having a purity of 99.997% or more was melted at about 550 ° C., and as shown in Table 1, added so as to have a cadmium content of 5.0% by weight with respect to metallic zinc. Then, a zinc alloy was prepared, and was sprayed in the same manner as in Example 1 to be pulverized.
【００２６】得られた５重量％Ｃｄ−Ｚｎ合金粉末に、
大気中で少量の水酸化カリウム水溶液を散布し、上記合
金粉末を撹拌することにより、酸化反応が進行して少な
くとも表面層が酸化された酸化亜鉛合金粉末を作製し
た。なお、酸化の度合いは、図１に示されるような開閉
可能な容器を用いて亜鉛合金粉末と接触する大気量を制
限することで制御した。To the obtained 5 wt% Cd-Zn alloy powder,
By sprinkling a small amount of an aqueous potassium hydroxide solution in the air and stirring the alloy powder, a zinc oxide alloy powder in which the oxidation reaction proceeded and at least the surface layer was oxidized was produced. The degree of oxidation was controlled by limiting the amount of atmospheric air in contact with the zinc alloy powder using a container that can be opened and closed as shown in FIG.
【００２７】得られた酸化亜鉛合金粉末を用い、実施例
１と同様に負極活物質を調製し、さらに密閉型ニッケル
−亜鉛蓄電池を作製した。Using the obtained zinc oxide alloy powder, a negative electrode active material was prepared in the same manner as in Example 1, and further a sealed nickel-zinc storage battery was prepared.
【００２８】実施例３〜１２ 亜鉛合金としての含有合金成分が表１となるようにした
こと以外は、実施例１と同様にして実施例１と同容量の
密閉型ニッケル−亜鉛蓄電池電池を作製した。 Examples 3 to 12 A sealed nickel-zinc accumulator battery having the same capacity as in Example 1 was prepared in the same manner as in Example 1 except that the alloy components contained as zinc alloys were changed to those shown in Table 1. did.
【００２９】[0029]
【表１】 [Table 1]
【００３０】この実施例１〜１２で得られた表面層が酸
化された各酸化亜鉛合金粉末の酸化亜鉛層を以下の方法
によって測定した。The zinc oxide layers of the respective zinc oxide alloy powders obtained by oxidizing the surface layers obtained in Examples 1 to 12 were measured by the following method.
【００３１】すなわち塩化アンモニウムとアンモニア水
の混合水溶液中に、酸化亜鉛合金粉末を浸漬して表面の
亜鉛酸化物層を溶解して分析した。その結果、実施例１
〜１２では３０〜９０重量％の酸化割合であった。That is, the zinc oxide alloy powder was immersed in a mixed aqueous solution of ammonium chloride and ammonia water to dissolve the zinc oxide layer on the surface for analysis. As a result, Example 1
-12, the oxidation rate was 30 to 90% by weight.
【００３２】比較例１ 負極活物質の調製として金属亜鉛６０重量部に対して酸
化亜鉛４０重量部を加え混合した。 Comparative Example 1 To prepare a negative electrode active material, 40 parts by weight of zinc oxide was added and mixed with 60 parts by weight of metallic zinc.
【００３３】次に、実施例１と同様にして実施例１と同
容量の密閉型ニッケル−亜鉛蓄電池を作成した。Then, a sealed nickel-zinc storage battery having the same capacity as in Example 1 was prepared in the same manner as in Example 1.
【００３４】比較例２ 実施例４で作成した亜鉛合金（５重量％Ｓｎ−Ｚｎ）粉
末５０重量部、酸化亜鉛粉末４０重量部、金属亜鉛粉末
１０重量部を加え混合した。 Comparative Example 2 50 parts by weight of the zinc alloy (5% by weight Sn-Zn) powder prepared in Example 4, 40 parts by weight of zinc oxide powder and 10 parts by weight of metallic zinc powder were added and mixed.
【００３５】次に、実施例１と同様にして実施例１と同
容量の密閉型ニッケル−亜鉛蓄電池を作成した。Then, a sealed nickel-zinc storage battery having the same capacity as in Example 1 was prepared in the same manner as in Example 1.
【００３６】実験例 このようにして得られた実施例１〜１２の電池と比較例
１〜２の電池を用い、充電電流２００ｍＡで１０．５時
間充電し、放電電流２Ａで終止電圧０．５Ｖ迄放電する
という充放電サイクル試験を行なった。充放電サイクル
試験は、電池の容量が１Ａｈになるまで繰り返し行っ
た。結果を図２に示す。 Experimental Example Using the batteries of Examples 1 to 12 and the batteries of Comparative Examples 1 and 2 thus obtained, charging was performed at a charging current of 200 mA for 10.5 hours, and a final voltage of 0.5 V was obtained at a discharging current of 2 A. A charge / discharge cycle test of discharging up to was performed. The charge / discharge cycle test was repeated until the battery capacity reached 1 Ah. The results are shown in Figure 2.
【００３７】図２から明らかなように、比較例１〜２の
電池に比べて、実施例１〜１２の電池はサイクル特性が
大幅に改善されていることが分かる。As is clear from FIG. 2, the cycle characteristics of the batteries of Examples 1 to 12 are significantly improved as compared with the batteries of Comparative Examples 1 and 2.
【００３８】[0038]
【発明の効果】以上説明したように、本発明の酸化亜鉛
合金粉末をアルカリ亜鉛蓄電池の負極活物質の少なくと
も一部に用いることにより、デントライトショート等が
防止され、その結果、アルカリ蓄電池のサイクル特性が
大幅に改善される。As described above, by using the zinc oxide alloy powder of the present invention as at least a part of the negative electrode active material of an alkaline zinc storage battery, a dendrite short circuit or the like is prevented, and as a result, the cycle of the alkaline storage battery is prevented. The characteristics are greatly improved.
【図１】 本発明の製造方法の詳細を示すフローチャー
ト。FIG. 1 is a flowchart showing details of a manufacturing method of the present invention.
【図２】 実施例および比較例における電池容量および
放電回数の関係を示すグラフ。FIG. 2 is a graph showing the relationship between the battery capacity and the number of discharges in Examples and Comparative Examples.
Claims (5)
を特徴とするアルカリ亜鉛蓄電池用酸化亜鉛合金粉末。1. A zinc oxide alloy powder for an alkaline zinc storage battery, wherein at least a surface layer is oxidized.
Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂｉ、Ａｌから選ばれる少な
くとも１種の元素と亜鉛および不可避不純物からなる請
求項１に記載のアルカリ亜鉛蓄電池用酸化亜鉛合金粉
末。2. The zinc alloy powder is Cd, Pb, Sn,
The zinc oxide alloy powder for alkaline zinc storage batteries according to claim 1, comprising at least one element selected from In, Ga, Tl, Ca, Bi, and Al, zinc, and inevitable impurities.
水溶液を用いて表面層を酸化することを特徴とする酸化
亜鉛合金粉末の製造方法。3. A method for producing a zinc oxide alloy powder, which comprises oxidizing the surface layer of the zinc alloy powder with an aqueous potassium hydroxide solution in the atmosphere.
Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂｉ、Ａｌから選ばれる少な
くとも１種の元素と亜鉛および不可避不純物からなる請
求項３に記載のアルカリ亜鉛蓄電池用酸化亜鉛合金粉末
の製造方法。4. The zinc alloy powder is Cd, Pb, Sn,
The method for producing a zinc oxide alloy powder for an alkaline zinc storage battery according to claim 3, comprising at least one element selected from In, Ga, Tl, Ca, Bi, and Al, zinc, and inevitable impurities.
ｉ、Ａｌから選ばれる少なくとも１種の元素と亜鉛およ
び不可避不純物からなる亜鉛合金粉末、 （３）少なくとも表面層が酸化されてなり、Ｃｄ、Ｐ
ｂ、Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｃａ、Ｂｉ、Ａｌから選
ばれる少なくとも１種の元素と亜鉛および不可避不純物
からなる酸化亜鉛合金粉末、を負極活物質とするアルカ
リ亜鉛蓄電池。5. (1) Zinc metal powder, (2) Cd, Pb, Sn, In, Ga, Tl, Ca, B
Zinc alloy powder consisting of at least one element selected from i and Al, zinc and unavoidable impurities (3) At least the surface layer is oxidized to form Cd, P
An alkaline zinc storage battery using, as a negative electrode active material, at least one element selected from b, Sn, In, Ga, Tl, Ca, Bi and Al, and a zinc oxide alloy powder containing zinc and inevitable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6147006A JPH0773881A (en) | 1993-06-30 | 1994-06-07 | Zinc oxide alloy powder for alkaline zinc storage battery and manufacture thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18341493 | 1993-06-30 | ||
| JP5-183414 | 1993-06-30 | ||
| JP6147006A JPH0773881A (en) | 1993-06-30 | 1994-06-07 | Zinc oxide alloy powder for alkaline zinc storage battery and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0773881A true JPH0773881A (en) | 1995-03-17 |
Family
ID=26477687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6147006A Pending JPH0773881A (en) | 1993-06-30 | 1994-06-07 | Zinc oxide alloy powder for alkaline zinc storage battery and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0773881A (en) |
-
1994
- 1994-06-07 JP JP6147006A patent/JPH0773881A/en active Pending
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