JPH06124706A - Sealed nickel-zinc storage battery - Google Patents

Sealed nickel-zinc storage battery

Info

Publication number
JPH06124706A
JPH06124706A JP4296306A JP29630692A JPH06124706A JP H06124706 A JPH06124706 A JP H06124706A JP 4296306 A JP4296306 A JP 4296306A JP 29630692 A JP29630692 A JP 29630692A JP H06124706 A JPH06124706 A JP H06124706A
Authority
JP
Japan
Prior art keywords
zinc
storage battery
sealed nickel
particle size
nickel
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
Application number
JP4296306A
Other languages
Japanese (ja)
Inventor
Kazuya Okabe
一弥 岡部
Kenkichi Fujii
健吉 藤井
Yukio Fujita
幸雄 藤田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yuasa Corp
Original Assignee
Yuasa Corp
Yuasa Battery Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yuasa Corp, Yuasa Battery Corp filed Critical Yuasa Corp
Priority to JP4296306A priority Critical patent/JPH06124706A/en
Publication of JPH06124706A publication Critical patent/JPH06124706A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE:To provide a sealed nickel-zinc storage battery having the capability of restraining the generation of hydrogen without any addition of mercury and ensuring excellent characteristics in terms of shelf life and charge and discharge cycle lifetime. CONSTITUTION:This battery uses a negative electrode of zinc mainly composed of zinc metal powder having a grain size between 10 and 25mum and zinc oxide powder having a grain size of 0.3mum or more. The generation of hydrogen can be restrained by reducing the grain size of the zinc metal powder and as a result, charge and discharge cycle lifetime after shelving can be extended.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、密閉形ニッケル−亜鉛
蓄電池に関するもので、さらに詳しく言えば、その亜鉛
極の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed nickel-zinc storage battery, and more particularly to improvement of the zinc electrode.

【０００２】[0002]

【従来の技術】近年、ポータブルタイプやコードレスタ
イプのエレクトロニクス機器の普及により、再充電可能
な二次電池の需要が高まってきている。2. Description of the Related Art In recent years, the demand for rechargeable secondary batteries has increased with the spread of portable type and cordless type electronic devices.

【０００３】このような二次電池は、機器の小型化、軽
量化に伴ってエネルギー密度が高く、メンテナンスが容
易であるものが注目され、特に密閉形ニッケル−亜鉛蓄
電池が注目されている。Such secondary batteries have attracted attention because of their high energy density and easy maintenance due to the downsizing and weight reduction of equipment, and particularly the sealed nickel-zinc storage batteries.

【０００４】上記した密閉形ニッケル−亜鉛蓄電池にお
ける亜鉛負極は、亜鉛の溶解度が高いために充電時に亜
鉛のデンドライトが成長してセパレータの貫通ショート
を起こしたり、シェイプチェンジによって利用率が低下
するという問題があり、充放電サイクル寿命が短くなる
原因になっていた。Since the zinc negative electrode in the above sealed nickel-zinc storage battery has a high solubility of zinc, the dendrite of zinc grows during charging to cause a short-circuit through the separator, or the shape change causes a decrease in the utilization rate. Which is a cause of shortening the charge / discharge cycle life.

【０００５】従来、このようなデンドライトやシェイプ
チェンジの発生を防止するため、粒径が１〜１０μの金
属亜鉛と粒径が０．３μ以上の酸化亜鉛を用いて電着を
均一に行うことが提案されている。Conventionally, in order to prevent such dendrites and shape changes from occurring, metal zinc having a particle size of 1 to 10 μm and zinc oxide having a particle size of 0.3 μm or more have been used for uniform electrodeposition. Proposed.

【０００６】[0006]

【発明が解決しようとする課題】上記した従来の密閉形
ニッケル−亜鉛蓄電池では、金属亜鉛の粒径が小さいた
め、表面積が大きくなり、保存時に金属亜鉛の腐食によ
って水素を発生させやすく、水銀を添加してこのような
水素の発生を抑制していた。しかしながら、水銀を使用
することは環境上好ましいものではなく、水銀に代わる
他の物質も種々提案されているが、コスト面で満足でき
ないという問題があった。In the above-mentioned conventional sealed nickel-zinc storage battery, since the particle size of metallic zinc is small, the surface area is large, and hydrogen is easily generated due to corrosion of metallic zinc during storage, so that mercury is not generated. It was added to suppress the generation of such hydrogen. However, the use of mercury is not environmentally preferable, and various other substances in place of mercury have been proposed, but there was a problem that the cost was not satisfactory.

【０００７】[0007]

【課題を解決するための手段】上記課題を解決するた
め、本発明は、酸化亜鉛および金属亜鉛を主成分とする
亜鉛負極と、ニッケル正極と、前記亜鉛負極とニッケル
正極との間に介挿されたセパレータと、このセパレータ
に含浸された電解液とを有する極群からなる密閉形ニッ
ケル−亜鉛蓄電池において、金属亜鉛粉末の粒径が１０
〜２５μで、酸化亜鉛粉末の粒径が０．３μ以上である
ことを特徴とするものである。In order to solve the above problems, the present invention provides a zinc negative electrode containing zinc oxide and metallic zinc as main components, a nickel positive electrode, and an interposing between the zinc negative electrode and the nickel positive electrode. In a sealed nickel-zinc storage battery consisting of a group of electrodes having a charged separator and an electrolytic solution impregnated in the separator, the particle size of the metal zinc powder is 10
.About.25 .mu., And the particle size of the zinc oxide powder is 0.3 .mu.m or more.

【０００８】[0008]

【作 用】従って、本発明は、均一な電着を損なうこと
なく金属亜鉛の粒子の表面積を減少させることができる
ので、水素の発生を抑制することができる。[Operation] Therefore, according to the present invention, since the surface area of the metallic zinc particles can be reduced without impairing the uniform electrodeposition, the generation of hydrogen can be suppressed.

【０００９】また、本発明は、金属亜鉛のＢＥＴ法によ
る比表面積が０．１ｍ2 ／ｇ以下にすることにより、そ
の表面積の増大を小さくすることができる。Further, according to the present invention, by increasing the specific surface area of metallic zinc by the BET method to 0.1 m 2 / g or less, the increase in the surface area can be reduced.

【００１０】また、本発明は、酸化亜鉛粉末の粒径を
０．３μ以上にしているので、接触による水素の発生を
抑制することができる。Further, according to the present invention, since the particle size of the zinc oxide powder is 0.3 μm or more, generation of hydrogen due to contact can be suppressed.

【００１１】[0011]

【実施例】以下本発明の詳細を実施例により説明する。EXAMPLES The details of the present invention will be described below with reference to examples.

【００１２】本発明の密閉形ニッケル−亜鉛蓄電池に用
いる亜鉛負極は、粒径が１０〜２５μ（平均粒径１７
μ）の金属亜鉛粉末２０重量％と、粒径が０．３μ以上
の酸化亜鉛粉末８０重量％とにポリテトラフルオロエチ
レン粒子を混合し、エタノール等の有機溶媒を用いて混
練して乾燥させる。なお、上記金属亜鉛粉末は、還元雰
囲気下で金属亜鉛を蒸発させてから冷却して凝集したも
ので、得られる金属亜鉛粒子が球状であるため、その表
面積の増大を最小限にすることができ、ＢＥＴ法による
比表面積を０．１ｍ2 ／ｇ以下にすることによって水素
の発生を抑制することが可能である。The zinc negative electrode used in the sealed nickel-zinc storage battery of the present invention has a particle size of 10 to 25 μ (average particle size of 17).
20% by weight of metallic zinc powder of (μ) and 80% by weight of zinc oxide powder having a particle size of 0.3 μ or more are mixed with polytetrafluoroethylene particles, kneaded with an organic solvent such as ethanol and dried. The metallic zinc powder is obtained by evaporating metallic zinc in a reducing atmosphere and then cooling and agglomerating it. Since the resulting metallic zinc particles are spherical, the increase in the surface area can be minimized. It is possible to suppress the generation of hydrogen by setting the specific surface area by the BET method to 0.1 m 2 / g or less.

【００１３】上記乾燥時に金属亜鉛が酸化してその微粒
子が金属亜鉛の表面に形成されないようにするため、前
記溶媒からできるだけ水を除去してからペースト状にす
る。In order to prevent the metallic zinc from being oxidized and forming fine particles on the surface of the metallic zinc during the above drying, water is removed from the solvent as much as possible and then the paste is formed.

【００１４】次に、上記ペーストを厚みが０．１ｍｍの
銅集電体に塗布し、乾燥、プレスして厚みが１ｍｍ、活
物質密度が２．０〜３．８ｇ／ｃｍ3 の亜鉛負極とす
る。Next, the paste is applied to a copper current collector having a thickness of 0.1 mm, dried and pressed to form a zinc negative electrode having a thickness of 1 mm and an active material density of 2.0 to 3.8 g / cm 3. To do.

【００１５】こうして得られた亜鉛負極４枚と、シンタ
ー式ニッケル正極３枚とに微孔性ポリプロピレンセパレ
ータとセルロースとを組み合わせた補液層を挟んで配置
し、電解液として比重が１．３〜１．４の水酸化リチウ
ムを添加した水酸化カリウム水溶液を用いて容量が７Ａ
ｈの本発明の密閉形ニッケル−亜鉛蓄電池を製作した。The thus-obtained four zinc negative electrodes and three sinter-type nickel positive electrodes are arranged with a replenisher layer composed of a combination of a microporous polypropylene separator and cellulose sandwiched therebetween, and the specific gravity of the electrolyte is 1.3 to 1 Using an aqueous solution of potassium hydroxide to which lithium hydroxide of 4 is added, the capacity is 7A.
The sealed nickel-zinc storage battery of the present invention of h was manufactured.

【００１６】上記した本発明電池Ａと、同じ方法で得た
粒径が１〜１０μ（平均粒径４μ、比表面積０．３６ｍ
2 ／ｇ）の金属亜鉛を用いた比較電池Ｂと、還元雰囲気
下で溶融亜鉛をノズルから噴霧して得た粒径が４０〜７
４μの金属亜鉛（比表面積０．０８ｍ2 ／ｇ）を用いた
従来電池Ｃと、上記本発明電池Ａに用いた金属亜鉛の１
０％を空気酸化して０．３μ以下の酸化亜鉛を形成して
なる比較電池Ｄと、還元雰囲気下で金属亜鉛を蒸発させ
てから冷却して凝集した粒径が２５〜４０μ（平均粒径
３５μ、比表面積０．０７ｍ2 ／ｇ）の金属亜鉛を用い
た比較電池Ｅとについて、充放電サイクル数、保存特性
を調査した。なお、還元雰囲気下で溶融亜鉛をノズルか
ら噴霧して得た金属亜鉛は、粒子の粒径が４０μ以上と
いう大粒子になるという特徴がある。The particle size obtained by the same method as the battery A of the present invention was 1 to 10 μ (average particle size 4 μ, specific surface area 0.36 m).
2 / g) of comparative battery B using metallic zinc and a particle size of 40 to 7 obtained by spraying molten zinc from a nozzle under a reducing atmosphere.
1 of the conventional battery C using 4 μm of metallic zinc (specific surface area 0.08 m 2 / g) and the metallic zinc used in the battery A of the present invention.
Comparative battery D in which 0% is air-oxidized to form zinc oxide of 0.3 μm or less, and the particle size of agglomerated by cooling after evaporating metallic zinc in a reducing atmosphere is 25 to 40 μm (average particle size The number of charge / discharge cycles and the storage characteristics of the comparative battery E using metallic zinc having a thickness of 35 μ and a specific surface area of 0.07 m 2 / g) were investigated. The metallic zinc obtained by spraying molten zinc from a nozzle under a reducing atmosphere is characterized in that it has a large particle size of 40 μm or more.

【００１７】図１は、上記各電池について、周囲温度２
５℃において、放電電流を１．４Ａ、放電深度を１００
％とし、充電電流を０．７Ａ、充電量を放電量の１０５
％とした時の充放電サイクル数と放電容量との関係を示
したものである。FIG. 1 shows the ambient temperature 2 for each of the above batteries.
At 5 ° C, the discharge current is 1.4A and the discharge depth is 100.
%, The charging current is 0.7 A, and the charging amount is 105% of the discharging amount.
It shows the relationship between the number of charge / discharge cycles and the discharge capacity when it is defined as%.

【００１８】図１から、本発明電池Ａと、比較電池Ｂ，
Ｄは充放電サイクル数が２５０サイクル以上になること
がわかる。From FIG. 1, the battery A of the present invention and the comparative battery B,
It can be seen that D has a charge / discharge cycle number of 250 or more.

【００１９】図２は、上記各電池について、周囲温度６
０℃において、２０日間放置した時の重量の変化を示し
たものである。FIG. 2 shows an ambient temperature of 6 for each of the above batteries.
It shows the change in weight when left for 20 days at 0 ° C.

【００２０】図２から、本発明電池Ａと比較電池Ｅとは
ほとんど重量の変化がないことがわかる。このことは、
還元雰囲気下で溶融金属亜鉛を蒸発させてから冷却して
凝集することによって得た粒子の比表面積が０．１ｍ2
／ｇ以下であり、このような金属亜鉛粒子を用いた場合
には水素の発生量を少なくできることを意味している。It can be seen from FIG. 2 that the battery A of the present invention and the comparative battery E show almost no change in weight. This is
The specific surface area of the particles obtained by evaporating the molten metal zinc in a reducing atmosphere, then cooling and agglomerating is 0.1 m 2
/ G or less, which means that the amount of hydrogen generated can be reduced when such metal zinc particles are used.

【００２１】図３は、上記放置した電池について、周囲
温度２５℃において、放電電流を１．４Ａ、放電深度を
１００％とし、充電電流を０．７Ａ、充電量を放電量の
１０５％とした時の放電容量の関係を示したものであ
る。FIG. 3 shows the discharge current of the above left battery at 25 ° C., the discharge current was 1.4 A, the discharge depth was 100%, the charge current was 0.7 A, and the charge amount was 105% of the discharge amount. It shows the relationship of the discharge capacity at the time.

【００２２】図３から、本発明電池Ａは放置後の性能も
優れていることがわかる。It can be seen from FIG. 3 that the battery A of the present invention has excellent performance after being left alone.

【００２３】上記した結果から、本発明電池Ａは、金属
亜鉛の表面積を小さくしたことにより、水素の発生を抑
制することができ、これによって放置後の充放電サイク
ル寿命を向上させることができる。From the above results, in the battery A of the present invention, generation of hydrogen can be suppressed by reducing the surface area of the metallic zinc, and thereby the charge / discharge cycle life after leaving can be improved.

【００２４】[0024]

【発明の効果】上記した如く、本発明の密閉形ニッケル
−亜鉛蓄電池は、保存特性と充放電サイクル寿命とにす
ぐれ、しかも水銀を添加しなくても水素の発生を抑制す
ることができる。As described above, the sealed nickel-zinc storage battery of the present invention has excellent storage characteristics and charge / discharge cycle life, and can suppress the generation of hydrogen without adding mercury.

【図面の簡単な説明】[Brief description of drawings]

【図１】充放電サイクル数と放電容量との関係を示した
図である。FIG. 1 is a diagram showing the relationship between the number of charge / discharge cycles and the discharge capacity.

【図２】放置後の重量変化の関係を示した図である。FIG. 2 is a diagram showing a relationship of a change in weight after standing.

【図３】放置後の充放電サイクル数と放電容量との関係
を示した図である。FIG. 3 is a diagram showing a relationship between the number of charge / discharge cycles after leaving and the discharge capacity.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 酸化亜鉛及び金属亜鉛を主成分とする亜
鉛負極と、ニッケル正極と、前記亜鉛負極とニッケル正
極との間に介挿されたセパレータと、このセパレータに
含浸された電解液とを有する極群からなる密閉形ニッケ
ル−亜鉛蓄電池において、金属亜鉛粉末の粒径が１０〜
２５μで、酸化亜鉛粉末の粒径が０．３μ以上であるこ
とを特徴とする密閉形ニッケル−亜鉛蓄電池。1. A zinc negative electrode containing zinc oxide and metallic zinc as main components, a nickel positive electrode, a separator interposed between the zinc negative electrode and the nickel positive electrode, and an electrolytic solution impregnated in the separator. In the sealed nickel-zinc storage battery including the group of poles, the metal zinc powder has a particle size of 10 to 10
A sealed nickel-zinc storage battery, characterized in that the particle size of the zinc oxide powder is 25 μm and 0.3 μm or more. 【請求項２】 金属亜鉛のＢＥＴ法による比表面積が
０．１ｍ2 ／ｇ以下であることを特徴とする請求項第１
項記載の密閉形ニッケル−亜鉛蓄電池。2. The specific surface area of metallic zinc according to the BET method is 0.1 m 2 / g or less.
The sealed nickel-zinc storage battery according to the item.
JP4296306A 1992-10-07 1992-10-07 Sealed nickel-zinc storage battery Pending JPH06124706A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4296306A JPH06124706A (en) 1992-10-07 1992-10-07 Sealed nickel-zinc storage battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4296306A JPH06124706A (en) 1992-10-07 1992-10-07 Sealed nickel-zinc storage battery

Publications (1)

Publication Number Publication Date
JPH06124706A true JPH06124706A (en) 1994-05-06

Family

ID=17831847

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4296306A Pending JPH06124706A (en) 1992-10-07 1992-10-07 Sealed nickel-zinc storage battery

Country Status (1)

Country Link
JP (1) JPH06124706A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002035617A3 (en) * 2000-10-06 2002-12-05 Pk Bauelemente Rechargeable zinc nickel battery
JP2015046335A (en) * 2013-08-29 2015-03-12 独立行政法人国立高等専門学校機構 Zinc secondary battery suppressed in generation of dendrite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002035617A3 (en) * 2000-10-06 2002-12-05 Pk Bauelemente Rechargeable zinc nickel battery
JP2015046335A (en) * 2013-08-29 2015-03-12 独立行政法人国立高等専門学校機構 Zinc secondary battery suppressed in generation of dendrite

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