JPH08241713A - Non-sintered nickel electrode for alkaline storage battery - Google Patents
Non-sintered nickel electrode for alkaline storage batteryInfo
- Publication number
- JPH08241713A JPH08241713A JP7045675A JP4567595A JPH08241713A JP H08241713 A JPH08241713 A JP H08241713A JP 7045675 A JP7045675 A JP 7045675A JP 4567595 A JP4567595 A JP 4567595A JP H08241713 A JPH08241713 A JP H08241713A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- weight
- cobalt
- mixed precipitate
- storage battery
- Prior art date
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Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケル−水素蓄電
池、ニッケル−カドミウム蓄電池に代表されるアルカリ
電池の正極として使用される非焼結式ニッケル極および
これに用いる活物質、更にはその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-sintered nickel electrode used as a positive electrode for alkaline batteries represented by nickel-hydrogen storage batteries and nickel-cadmium storage batteries, an active material used therefor, and a method for producing the same. It is about.
【０００２】[0002]
【従来の技術】従来、アルカリ電池用ニッケル極として
は、芯金である穿穴鋼板等にニッケル粉末を焼結させて
得た基板に活物質を含浸させて使用する、所謂焼結式極
板が知られている。この極板は、ニッケル粉末間の結合
が弱く、基板を高多孔度とした場合にはニッケル粉末の
脱落を生じるために、実用上基板の多孔度を80％程度と
するのが限界であった。2. Description of the Related Art Conventionally, as a nickel electrode for an alkaline battery, a so-called sintered electrode plate is used which is obtained by impregnating a substrate obtained by sintering nickel powder on a cored steel plate which is a core metal with an active material. It has been known. In this electrode plate, the bond between nickel powders is weak, and when the substrate is made to have high porosity, the nickel powder comes off. Therefore, the porosity of the substrate was practically limited to about 80%. .
【０００３】また、穿孔鋼板等の芯金を必要とすること
から、一般に活物質の充填密度が小さくなる。更に、焼
結により形成されたニッケル粉末の細孔は、10μｍ以下
と小さいため、活物質の充填方法については、煩雑な工
程を数サイクルも繰り返す溶液含浸法に限定される等の
問題点がある。Further, since a cored bar such as a perforated steel plate is required, the packing density of the active material is generally low. Further, since the pores of the nickel powder formed by sintering are as small as 10 μm or less, there is a problem that the method of filling the active material is limited to the solution impregnation method in which complicated steps are repeated for several cycles. .
【０００４】これらの問題点を改良する試みとして、例
えば芯金を用いない耐アルカリ性金属繊維焼結体、ある
いは炭素繊維不織布等に耐アルカリ性金属をメッキし導
電芯体を得、ここに水酸化ニッケル活物質粉末をペース
ト状として充填する所謂ペースト式極板が開発されてい
る。この極板であっても、前記焼結式極板に比べ、活物
質の利用率が低く、実用上問題があった。In an attempt to improve these problems, for example, an alkali-resistant metal fiber sintered body which does not use a core metal, or a carbon fiber nonwoven fabric is plated with an alkali-resistant metal to obtain a conductive core body, and nickel hydroxide is added thereto. A so-called paste type electrode plate in which the active material powder is filled as a paste has been developed. Even with this electrode plate, the utilization factor of the active material was lower than that of the above-mentioned sintered electrode plate, and there was a practical problem.
【０００５】この対策として、コバルトを活物質の表面
に存在させるという技術が知られている。具体的には、
アルカリ電解液中でコバルト化合物を溶解させ、活物質
の表面に２価のHCoO2-を生成させる。これが貴な電位に
おいて導電性を有するCoOOH化合物に変化するように、
活物質表面をコバルト化合物でコーティングしなければ
ならない。例えば特開昭62-234867号公報や特開昭62-23
7667号公報に開示されるように、水酸化ニッケル粒子表
面を水酸化コバルトで被覆した方法や、特開平3-62457
号公報に開示されるように、水酸化ニッケル粒子表面を
水酸化ニッケル及び水酸化コバルトの固溶体で被覆した
方法が提案されている。As a countermeasure against this, a technique is known in which cobalt is allowed to exist on the surface of the active material. In particular,
A cobalt compound is dissolved in an alkaline electrolyte to form divalent HCoO 2- on the surface of the active material. As this changes into a CoOOH compound with conductivity at noble potential,
The active material surface must be coated with a cobalt compound. For example, JP-A-62-234867 and JP-A-62-23
As disclosed in Japanese Patent No. 7667, a method of coating the surface of nickel hydroxide particles with cobalt hydroxide, and JP-A-3-62457.
As disclosed in the publication, a method has been proposed in which the surface of nickel hydroxide particles is coated with a solid solution of nickel hydroxide and cobalt hydroxide.
【０００６】然し乍ら、上述したような方法で作製され
た活物質である水酸化ニッケル粒子は、表面を被覆して
いるコバルトが、電池のサイクル進行に伴い、水酸化ニ
ッケル粒子内に拡散していく。この結果、コバルトの添
加効果である電極表面の導電性を高めることがサイクル
長期に亘って維持することができず、サイクル進行に伴
い容量が低下してしまうという問題があった。However, the nickel hydroxide particles which are the active material produced by the above-mentioned method, the cobalt coating the surface thereof diffuses into the nickel hydroxide particles as the battery cycle progresses. . As a result, there is a problem in that it is not possible to maintain the conductivity of the electrode surface, which is the effect of adding cobalt, for a long period of the cycle, and the capacity decreases as the cycle progresses.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、かかる問題
点を解決すべくなされたものであって、コバルトが水酸
化ニッケル粒子中へ拡散するのを抑え、サイクル長期に
亘ってコバルトの添加効果が発揮される活物質を提案す
るものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and suppresses the diffusion of cobalt into nickel hydroxide particles, and the effect of adding cobalt over a long cycle time. It proposes an active material in which
【０００８】また、この活物質を用い高性能かつ安定で
生産性の高いアルカリ電池用非焼結式ニッケル極を提供
するものである。この結果、サイクル特性に優れたアル
カリ蓄電池が提供できる。Further, the present invention provides a non-sintered nickel electrode for alkaline batteries, which uses this active material and has high performance, stability and high productivity. As a result, an alkaline storage battery having excellent cycle characteristics can be provided.
【０００９】更には、かかる活物質及びこれを用いた非
焼結式ニッケル極の製造方法を提案するものである。Furthermore, the present invention proposes a method for producing such an active material and a non-sintered nickel electrode using the same.
【００１０】[0010]
【課題を解決するための手段】本発明のアルカリ蓄電池
用非焼結式ニッケル極は、水酸化ニッケルを主体とする
粒子と、マンガン及びコバルトを含む混合析出物とから
なる活物質を用いたニッケル極であって、前記粒子が前
記混合析出物にて被覆されたことを特徴とする。The non-sintered nickel electrode for an alkaline storage battery of the present invention is a nickel using an active material composed of particles mainly containing nickel hydroxide and a mixed precipitate containing manganese and cobalt. It is a pole and the particles are coated with the mixed precipitate.
【００１１】また本発明のアルカリ蓄電池に用いる非焼
結式ニッケル極用活物質は、水酸化ニッケルを主体とす
る粒子と、マンガン及びコバルトを含む混合析出物とか
らなる活物質であって、前記粒子が前記混合析出物にて
被覆されたことを特徴とする。The non-sintered nickel electrode active material used in the alkaline storage battery of the present invention is an active material composed of particles containing nickel hydroxide as a main component and a mixed precipitate containing manganese and cobalt. The particles are coated with the mixed precipitate.
【００１２】そして、本発明のアルカリ蓄電池に用いる
非焼結式ニッケル極用活物質の製造方法は、水酸化ニッ
ケルを主体とする粒子を、マンガン塩溶液とコバルト塩
溶液とからなる混合溶液中に浸漬し、中和を行い、マン
ガン及びコバルトからなる混合析出物にて前記粒子を被
覆したことを特徴とする。Then, the method for producing the non-sintered nickel electrode active material used in the alkaline storage battery of the present invention is such that particles containing nickel hydroxide as a main component are mixed in a mixed solution of a manganese salt solution and a cobalt salt solution. It is characterized in that the particles are immersed, neutralized, and coated with a mixed precipitate of manganese and cobalt.
【００１３】更に、本発明のアルカリ蓄電池用非焼結式
ニッケル極の製造方法は、水酸化ニッケルを主体とする
粒子を、マンガン塩溶液とコバルト塩溶液とからなる混
合溶液中に浸漬し、中和を行い、マンガン及びコバルト
からなる混合析出物にて前記粒子を被覆した活物質を
得、この活物質を導電芯体に充填することを特徴とす
る。Further, according to the method for producing a non-sintered nickel electrode for an alkaline storage battery of the present invention, particles mainly composed of nickel hydroxide are immersed in a mixed solution of a manganese salt solution and a cobalt salt solution, It is characterized that the active material is obtained by coating the particles with a mixed precipitate of manganese and cobalt, and filling the conductive core with the active material.
【００１４】上記本発明において、上記混合析出物が、
上記活物質の重量に対して、２重量％〜26重量％の範
囲、特に好ましくは３重量％〜25重量％の範囲とする。In the present invention, the mixed precipitate is
The range is 2 to 26% by weight, particularly preferably 3 to 25% by weight, based on the weight of the active material.
【００１５】また、上記本発明において、マンガンが、
混合析出物においてコバルトに対する金属換算量で、0.
5重量％〜50重量％の範囲となるように添加する。In the present invention, manganese is
The amount of metal equivalent to cobalt in the mixed precipitate is 0.
It is added so as to be in the range of 5% by weight to 50% by weight.
【００１６】尚、上記本発明の製造方法において、マン
ガン塩としては、硫酸マンガン、硝酸マンガンが用いら
れ、コバルト塩としては、硫酸コバルト、硝酸コバルト
が使用可能である。このような硫酸塩、硝酸塩を使用す
ることにより、不純物が混入することなく効率よく、活
物質及びニッケル極が提供できる。In the manufacturing method of the present invention, manganese sulfate and manganese nitrate are used as the manganese salt, and cobalt sulfate and cobalt nitrate can be used as the cobalt salt. By using such a sulfate or nitrate, an active material and a nickel electrode can be efficiently provided without mixing impurities.
【００１７】[0017]
【作用】水酸化ニッケル粒子または水酸化ニッケルを主
成分とする粒子表面を、マンガン及びコバルトとを含有
する混合析出物にて被覆する。この結果、電池のサイク
ル数が進行しても、活物質の表面へ添加したコバルト
が、粒子内へ拡散することが防止できる。そのため、コ
バルトの添加効果が長期に亘って発揮でき、サイクル進
行に伴う電池容量の低下が防止できる。Function: The surface of the nickel hydroxide particles or the particles containing nickel hydroxide as the main component is coated with a mixed precipitate containing manganese and cobalt. As a result, it is possible to prevent the cobalt added to the surface of the active material from diffusing into the particles even if the cycle number of the battery progresses. Therefore, the effect of adding cobalt can be exerted for a long period of time, and the decrease in battery capacity due to the progress of cycles can be prevented.
【００１８】この理由は明らかではないが、マンガン及
びコバルトとを含有する混合析出物であれば、少なくと
も一部は水酸化マンガンと水酸化コバルトとの混晶とな
っている。そして、この混晶であれば、電池のサイクル
数が進行しても、混晶の結晶構造が維持される。この結
果、活物質としての水酸化ニッケルへコバルトの拡散が
抑制されると推定される。Although the reason for this is not clear, at least a part of the mixed precipitate containing manganese and cobalt is a mixed crystal of manganese hydroxide and cobalt hydroxide. With this mixed crystal, the crystal structure of the mixed crystal is maintained even when the number of battery cycles is increased. As a result, it is presumed that the diffusion of cobalt into nickel hydroxide as the active material is suppressed.
【００１９】活物質に形成された混合析出物においてコ
バルトに対する金属換算量で、マンガンを0.5重量％未
満添加しただけでは、水酸化ニッケル粒子内へコバルト
が拡散するのを抑制できない。そのため、サイクル進行
に伴うに電池容量の低下が認められる。一方、マンガン
を50重量％を越えて添加した場合には、活物質表面の導
電性が低下するため、十分な放電容量即ち電池容量が得
られない。It is not possible to suppress the diffusion of cobalt into the nickel hydroxide particles by only adding less than 0.5% by weight of manganese in the mixed precipitate formed on the active material, in terms of metal equivalent to cobalt. Therefore, the battery capacity is reduced as the cycle progresses. On the other hand, when manganese is added in an amount of more than 50% by weight, the conductivity of the surface of the active material is lowered, so that sufficient discharge capacity, that is, battery capacity cannot be obtained.
【００２０】また、混合析出物が、活物質の全重量に対
して、３重量％未満では、コバルトの被覆効果が十分で
なく、電極の導電性を高めることができなくなる。一
方、25重量％を越える被覆では、活物質において水酸化
ニッケルの比率が減少してしまい、十分な電池容量を得
ることができない。If the mixed precipitate is less than 3% by weight based on the total weight of the active material, the cobalt coating effect is not sufficient and the conductivity of the electrode cannot be increased. On the other hand, if the coating amount exceeds 25% by weight, the proportion of nickel hydroxide in the active material decreases, and a sufficient battery capacity cannot be obtained.
【００２１】[0021]
【実施例】 （実施例１） ［活物質の作製］硫酸コバルト（16.8ｇ）及び硫酸マン
ガン（2.8ｇ）とを溶解した水溶液を1000ｍｌ用意す
る。この水溶液に、水酸化ニッケル粒子であるNi(OH)2
粉末（100ｇ）を投入、撹拌する。これと同時に、１Ｍ
水酸化ナトリウム水溶液を滴下し、中和を行った。この
時のｐＨは、12に調節、保持されている。尚、撹拌時間
は、１時間である。その後、表面に混合析出物が形成さ
れた水酸化ニッケル粒子を、水にて洗浄後、真空乾燥を
行い、本発明の活物質とした。Example 1 Preparation of Active Material 1000 ml of an aqueous solution in which cobalt sulfate (16.8 g) and manganese sulfate (2.8 g) are dissolved is prepared. In this aqueous solution, nickel hydroxide particles Ni (OH) 2
Add powder (100 g) and stir. At the same time, 1M
An aqueous solution of sodium hydroxide was added dropwise for neutralization. The pH at this time is adjusted and maintained at 12. The stirring time is 1 hour. After that, the nickel hydroxide particles on the surface of which mixed precipitates were formed were washed with water and vacuum dried to obtain the active material of the present invention.
【００２２】尚、この活物質は、活物質表面に形成され
た混合析出物として、水酸化コバルト及び水酸化マンガ
ンが析出している。この混合析出物は、活物質重量に対
して10重量％である。そして、混合析出物においては、
その中のコバルトに対して金属換算でマンガン10重量％
を含有している。In this active material, cobalt hydroxide and manganese hydroxide are deposited as a mixed deposit formed on the surface of the active material. This mixed precipitate is 10% by weight based on the weight of the active material. And in the mixed precipitate,
10% by weight of manganese in terms of metal relative to cobalt in it
It contains.
【００２３】活物質作製時のｐＨ測定には、自動温度補
償付きガラス電極ｐＨメータを用いている。 ［電極の作製］上述の活物質の作製で得た活物質80重量
％と、結着剤若しくは増粘剤としてのメチルセルロース
（１重量％含有）水溶液20重量％とを混練してペースト
をえた。このペーストを、ニッケルメッキを施した発泡
メタル（多孔度95％、平均粒径200μｍ）からなる多孔
体である導電芯体に充填した。そして、このペーストが
充填された導電芯体を乾燥後、成形することで、非焼結
式ニッケル極を得た。 ［電池の作製］上述のようにして得られた非焼結式ニッ
ケル極を正極とし、公知のペースト式カドミウム極、ナ
イロン不織布からなるセパレータ、アルカリ電解液、金
属製電池容器、金属蓋の各パーツを組合わせて、本発明
にかかるニッケル−カドミウム電池を作製した。ここで
使用したアルカリ電解液の組成は、KOH：NaOH：LiOH＝
８：１：１（比重＝1.285）である。A glass electrode pH meter with automatic temperature compensation is used for measuring the pH during the production of the active material. [Production of Electrode] 80% by weight of the active material obtained in the above-described production of the active material was mixed with 20% by weight of an aqueous solution of methylcellulose (containing 1% by weight) as a binder or a thickener to obtain a paste. This paste was filled in a conductive core body which was a porous body made of nickel-plated foam metal (porosity 95%, average particle size 200 μm). Then, the conductive core filled with this paste was dried and then molded to obtain a non-sintered nickel electrode. [Production of Battery] The non-sintered nickel electrode obtained as described above is used as a positive electrode, a known paste-type cadmium electrode, a separator made of nylon nonwoven fabric, an alkaline electrolyte, a metal battery container, and a metal lid part. Was combined to produce a nickel-cadmium battery according to the present invention. The composition of the alkaline electrolyte used here is KOH: NaOH: LiOH =
It is 8: 1: 1 (specific gravity = 1.285).
【００２４】このようにして、コバルト及びマンガンの
混合析出物、即ち混晶にて被覆された活物質を用いた電
池を、本発明電池Ａとした。 （比較例１）比較例として、硫酸コバルト（18.5ｇ）を
溶解したコバルト水溶液1000ｍｌを準備する。このコバ
ルト水溶液に、上記で使用した水酸化ニッケル粒子であ
るNi(OH)2粉末（100ｇ）を撹拌しながら投入した。ここ
に１Ｍ水酸化ナトリウム水溶液を滴下し、中和を行っ
た。この時のｐＨは、12に調節、保持されている。この
撹拌、混合には、１時間を要している。この時のコバル
ト化合物即ち水酸化コバルトからなる析出物は、活物質
の重量に対して10重量％である。A battery using an active material coated with a mixed precipitate of cobalt and manganese, that is, a mixed crystal in this manner was designated as Battery A of the present invention. (Comparative Example 1) As a comparative example, 1000 ml of an aqueous cobalt solution in which cobalt sulfate (18.5 g) is dissolved is prepared. Ni (OH) 2 powder (100 g), which was the nickel hydroxide particles used above, was added to this aqueous cobalt solution while stirring. A 1 M aqueous sodium hydroxide solution was added dropwise to neutralize. The pH at this time is adjusted and maintained at 12. One hour is required for this stirring and mixing. At this time, the cobalt compound, that is, the precipitate composed of cobalt hydroxide is 10% by weight based on the weight of the active material.
【００２５】その後、水酸化コバルトにより被覆された
水酸化ニッケル粒子の沈殿物を得、水洗後、乾燥して、
比較例１の活物質を得た。そして上述の実施例１と同様
にして、比較電池Ｘを作製した。Thereafter, a precipitate of nickel hydroxide particles coated with cobalt hydroxide was obtained, washed with water and dried,
An active material of Comparative Example 1 was obtained. Then, a comparative battery X was prepared in the same manner as in Example 1 described above.
【００２６】尚、この比較例１は、水酸化コバルトによ
り被覆された水酸化ニッケル粒子を使用するという意味
で、特開昭62-234867号公報に開示された技術に近い方
法である。 （比較例２）硫酸コバルト（16.7ｇ）、硫酸ニッケル
（1.85ｇ）を溶解した水溶液1000ｍｌを準備する。この
水溶液に、上記同様にして水酸化ニッケル粒子であるNi
(OH)2粉末（100ｇ）を撹拌しながら投入した。そして、
ここへ１Ｍ水酸化ナトリウム水溶液を滴下し、中和を行
った。この時のｐＨは、12に調節、保持されている。こ
の混合、撹拌には、１時間を要した。この時の表面析出
物は、活物質の重量に対して10重量％である。また、そ
の中のコバルトに対して、金属換算でニッケルが10重量
％含有されている。Comparative Example 1 is a method close to the technique disclosed in Japanese Patent Laid-Open No. 62-234867 in the sense that nickel hydroxide particles coated with cobalt hydroxide are used. Comparative Example 2 1000 ml of an aqueous solution in which cobalt sulfate (16.7 g) and nickel sulfate (1.85 g) are dissolved is prepared. In this aqueous solution, nickel hydroxide particles Ni
(OH) 2 powder (100 g) was added with stirring. And
A 1 M aqueous sodium hydroxide solution was added dropwise to neutralize the solution. The pH at this time is adjusted and maintained at 12. One hour was required for this mixing and stirring. The surface deposit at this time is 10% by weight with respect to the weight of the active material. In addition, nickel is contained in an amount of 10% by weight in terms of metal with respect to cobalt in the alloy.
【００２７】その後、水酸化コバルト及び水酸化ニッケ
ルにより被覆された水酸化ニッケル粒子の沈殿物を得、
水洗後、乾燥して、比較例２としての活物質を得た。Thereafter, a precipitate of nickel hydroxide particles coated with cobalt hydroxide and nickel hydroxide was obtained,
After washing with water and drying, an active material as Comparative Example 2 was obtained.
【００２８】そして、この活物質を用い、上述の実施例
１と同様にして、比較電池Ｙを作製した。Then, using this active material, a comparative battery Y was prepared in the same manner as in Example 1 described above.
【００２９】尚、この比較例２は、水酸化コバルトと水
酸化ニッケルの固溶体により被覆された水酸化ニッケル
粒子を使用するという意味で、特開平3ー62457号公報に
開示された技術に近い方法である。 ［電池の試験条件］このようにして得られた本発明電池
Ａ、比較電池Ｘ、比較電池Ｙを用い、電池のサイクル特
性を比較した。この時の実験条件は、各電池を、0.1Ｃ
の電流で160％の深度まで充電し、１Ｃ放電（1.0Ｖカッ
ト）することを繰り返すというものである。そして、各
電池容量を実測した。In Comparative Example 2, nickel hydroxide particles coated with a solid solution of cobalt hydroxide and nickel hydroxide are used, and a method close to the technique disclosed in JP-A-3-62457 is used. Is. [Battery Test Conditions] The battery A of the present invention, comparative battery X, and comparative battery Y thus obtained were used to compare the cycle characteristics of the batteries. The experimental condition at this time is 0.1C for each battery.
The battery is charged up to a depth of 160% with this current and discharged 1C (1.0V cut) repeatedly. And each battery capacity was measured.
【００３０】図１に、この結果を示す。図１の横軸はサ
イクル数、縦軸は電池容量を示している。尚、この電池
容量は、１サイクル目の放電容量を100とした指数で示
している。これより、比較電池Ｘ及び比較電池Ｙでは、
サイクル数の進行に伴い、電池容量が低下するのに対し
て、本発明電池Ａではその劣化がほとんど観察されない
ことが理解できる。The results are shown in FIG. The horizontal axis of FIG. 1 represents the number of cycles and the vertical axis represents the battery capacity. The battery capacity is indicated by an index with the discharge capacity in the first cycle as 100. From this, in the comparative battery X and the comparative battery Y,
It can be understood that the battery capacity decreases as the number of cycles progresses, whereas the deterioration is hardly observed in the battery A of the present invention.
【００３１】このようにサイクル特性に差が観察される
理由は、本発明電池Ａでは活物質表面へ添加したコバル
トが水酸化ニッケル粒子内へ拡散するのが防止されてい
ることに起因する。この結果、コバルトの添加効果が長
期に亘って発揮でき、サイクル進行に伴う電池容量の低
下が防止されている。The reason why the difference in cycle characteristics is observed is that in the battery A of the present invention, the cobalt added to the surface of the active material is prevented from diffusing into the nickel hydroxide particles. As a result, the effect of adding cobalt can be exerted for a long period of time, and the decrease in battery capacity due to the progress of cycles is prevented.
【００３２】尚、上述した実施例１では、亜鉛、コバル
ト、カドミウム、カルシウム、マグネシウム、マンガン
等を含まない水酸化ニッケル粒子を出発物質として用い
ている。当然のことながら、亜鉛、コバルト、カドミウ
ム、マグネシウム、カルシウム、マンガン等を内部に固
溶させた水酸化ニッケルを主成分とする活物質を用い
て、コバルトとマンガンとの混合析出物を形成した場合
であっても、同様の効果が得られる。 （実施例２）この実施例２では、混合析出物を形成する
元素である、マンガンとコバルトの添加量について、検
討を行った。ここで用いた活物質は、上記実施例１の
［活物質の作製］に準じて、用意した。即ち、水に溶解
させたコバルト塩及びマンガン塩量を調整することによ
り、混合析出物におけるコバルト添加量を変化させてい
る。ここで、活物質の重量に対する混合析出物の重量比
率は、10重量％と固定している。In Example 1 described above, nickel hydroxide particles containing no zinc, cobalt, cadmium, calcium, magnesium, manganese, etc. are used as the starting material. As a matter of course, when a mixed precipitate of cobalt and manganese is formed by using an active material containing nickel hydroxide as a main component in which zinc, cobalt, cadmium, magnesium, calcium, manganese, etc. are solid-solved. However, the same effect can be obtained. (Example 2) In this Example 2, the amounts of manganese and cobalt, which are elements forming mixed precipitates, were examined. The active material used here was prepared according to [Preparation of active material] in Example 1 above. That is, the amount of cobalt added to the mixed precipitate is changed by adjusting the amounts of cobalt salt and manganese salt dissolved in water. Here, the weight ratio of the mixed precipitate to the weight of the active material is fixed at 10% by weight.
【００３３】具体的な添加量、即ち活物質表面に形成さ
れた混合析出物においてコバルトに対するマンガンの添
加量としては、0.10重量％、0.25重量％、0.5重量％、
１重量％、５重量％、10重量％、25重量％、35重量％、
50重量％、55重量％、60重量％である。このマンガン添
加量は、この混合析出物内において、コバルト量を金属
換算し、これを基準としている。The specific addition amount, that is, the addition amount of manganese to cobalt in the mixed precipitate formed on the surface of the active material is 0.10% by weight, 0.25% by weight, 0.5% by weight,
1% by weight, 5% by weight, 10% by weight, 25% by weight, 35% by weight,
50% by weight, 55% by weight and 60% by weight. The amount of manganese added is based on the amount of cobalt converted to metal in the mixed precipitate.
【００３４】これらの各活物質を用いて電池を作製し、
それぞれＢ1、Ｂ2、Ｂ3、Ｂ4、Ｂ5、Ｂ6、Ｂ7、Ｂ8、Ｂ
9、Ｂ10、Ｂ11とした。そして、上述した電池の試験条
件と、同様の条件にて、電池のサイクル試験を行った。A battery was prepared using each of these active materials,
B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , B 8 , B respectively
9 , B 10 , and B 11 . Then, a battery cycle test was performed under the same conditions as the above-described battery test conditions.
【００３５】図２に、この結果を示す。図２において、
横軸はサイクル数（回）、また縦軸は各電池の放電容量
を表している。ここで、電池の放電容量は、１サイクル
目の放電容量を100とした指数で示されている。The results are shown in FIG. In FIG.
The horizontal axis represents the number of cycles (times), and the vertical axis represents the discharge capacity of each battery. Here, the discharge capacity of the battery is shown by an index with the discharge capacity in the first cycle as 100.
【００３６】この図２より、コバルトに対するマンガン
の添加量が、金属換算で0.5重量％以上である電池Ｂ3〜
Ｂ11において、良好なサイクル特性が得られることがわ
かる。From FIG. 2, it can be seen from the battery B 3 that the addition amount of manganese to cobalt is 0.5% by weight or more in terms of metal.
It can be seen that good cycle characteristics can be obtained at B 11 .
【００３７】次に、各電池におけるマンガン添加量及び
各電池の放電容量を表１に示す。Next, Table 1 shows the amount of manganese added to each battery and the discharge capacity of each battery.
【００３８】[0038]
【表１】 [Table 1]
【００３９】この表１では、300サイクル目の放電容量
が、電池の放電容量として示されている。この値は、コ
バルトに対するマンガン添加量即ち含有量が、金属換算
で10重量％である電池Ｂ4の放電容量を100とした指数で
示している。表１より、マンガン添加量が50％を越えた
電池Ｂ10、Ｂ11では、電池の放電容量が低下しているこ
とがわかる。In Table 1, the discharge capacity at the 300th cycle is shown as the discharge capacity of the battery. This value is shown as an index with the discharge capacity of the battery B 4 having a manganese addition amount of cobalt, that is, a content of 10% by weight in terms of metal as 100. From Table 1, it can be seen that the discharge capacities of the batteries B 10 and B 11 in which the added amount of manganese exceeds 50% are lowered.
【００４０】以上より、マンガン添加量としては、活物
質表面に形成された混合析出物中のコバルトに対して、
金属換算で0.5重量％〜50重量％の範囲で添加されるの
が好ましいといえる。 （実施例３）この実施例３では、活物質の重量に対する
混合析出物の重量比率と、電池特性について、検討を行
った。From the above, the amount of manganese added is based on the cobalt in the mixed precipitate formed on the surface of the active material.
It can be said that it is preferably added in the range of 0.5% by weight to 50% by weight in terms of metal. (Example 3) In this example 3, the weight ratio of the mixed precipitate to the weight of the active material and the battery characteristics were examined.
【００４１】各活物質は、上記実施例１の［活物質の作
製］に準備したものである。即ち、コバルト塩、マンガ
ン塩の使用量を調整することにより、活物質に対する混
合析出物の重量比率を変化させている。ここで、混合析
出物中のコバルトに対するマンガンの添加量は、金属換
算で10重量％と固定されている。Each active material was prepared in [Preparation of Active Material] of Example 1 above. That is, the weight ratio of the mixed precipitate to the active material is changed by adjusting the amounts of cobalt salt and manganese salt used. Here, the addition amount of manganese to cobalt in the mixed precipitate is fixed at 10% by weight in terms of metal.
【００４２】具体的な各混合析出物の重量比率として
は、０重量％、２重量％、３重量％、５重量％、10重量
％、15重量％、20重量％、25重量％、26重量％、28重量
％、30重量％である。このような各活物質を用いて作製
した電池を、それぞれＣ1、Ｃ2、Ｃ3、Ｃ4、Ｃ5、Ｃ6、
Ｃ7、Ｃ8、Ｃ9、Ｃ10、Ｃ11とした。そして、上述した
電池の試験条件と、同様の条件にて、電池のサイクル試
験を行った。The specific weight ratio of each mixed precipitate is 0% by weight, 2% by weight, 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 26% by weight. %, 28% by weight, 30% by weight. Batteries produced by using such active materials are C 1 , C 2 , C 3 , C 4 , C 5 , C 6 ,
C 7 , C 8 , C 9 , C 10 , and C 11 were used. Then, a battery cycle test was performed under the same conditions as the above-described battery test conditions.
【００４３】図３に、この結果を示す。図３において、
横軸は活物質の重量に対する混合析出物の重量比率であ
り、縦軸は電池の放電容量を相対的に示したものであ
る。この放電容量は、各活物質に対する混合析出物の重
量比率が10重量％である活物質を用い作製した電池を基
準とし、この電池の１０サイクル目の放電容量を100と
した指数で相対的に表している。The results are shown in FIG. In FIG.
The horizontal axis represents the weight ratio of the mixed precipitate to the weight of the active material, and the vertical axis represents the discharge capacity of the battery. This discharge capacity is based on a battery manufactured using an active material in which the weight ratio of the mixed precipitate to each active material is 10% by weight, and is an index relative to the discharge capacity at the 10th cycle of this battery as 100 It represents.
【００４４】図３より、活物質の重量に対する混合析出
物の比率が、２重量％〜26重量％の範囲である電池Ｃ2
〜Ｃ9において、放電容量の向上が図られていることが
判る。From FIG. 3, the ratio of the mixed precipitate to the weight of the active material is in the range of 2% by weight to 26% by weight in the battery C 2
It can be seen that the discharge capacity is improved in the range from to C 9 .
【００４５】更に、３重量％〜25重量％の範囲である電
池Ｃ3〜Ｃ8においては、特に良好な放電容量が得られる
ことがわかる。[0045] Further, in the battery C 3 -C 8 ranges from 3% to 25% by weight, it can be seen that particularly good discharge capacity is obtained.
【００４６】以上より、混合析出物が、活物質の重量に
対して、２重量％〜26重量％の範囲で添加されたものが
好ましく、特に３重量％〜25重量％であれば最適である
ことが理解できる。From the above, the mixed precipitate is preferably added in the range of 2% by weight to 26% by weight, particularly 3% by weight to 25% by weight, based on the weight of the active material. I understand.
【００４７】[0047]
【発明の効果】以上の如く本発明によれば、活物質にお
いて、コバルトの水酸化ニッケル粒子中への拡散を抑
え、サイクル長期に亘ってコバルトの添加効果が発揮で
きる。また、かかる活物質を用いた非焼結式ニッケル極
は、サイクル長期に亘って高い容量が維持できる。As described above, according to the present invention, in the active material, the diffusion of cobalt into the nickel hydroxide particles can be suppressed, and the effect of adding cobalt can be exhibited for a long period of the cycle. Moreover, the non-sintered nickel electrode using such an active material can maintain a high capacity over a long period of the cycle.
【００４８】そして、本発明の製造方法によれば、この
ような活物質及び非焼結式ニッケル極が、不純物が混入
することなく効率よく製造できる。According to the manufacturing method of the present invention, such an active material and a non-sintered nickel electrode can be efficiently manufactured without mixing impurities.
【００４９】この結果、サイクル長期に亘って、コバル
トの添加効果が発揮され高容量を維持可能な、サイクル
特性に優れたアルカリ蓄電池が提供できるものであり、
その工業的価値は極めて大きい。As a result, it is possible to provide an alkaline storage battery which is excellent in cycle characteristics and which is capable of maintaining the high capacity by exhibiting the effect of adding cobalt over a long period of the cycle.
Its industrial value is extremely high.
【図１】電池のサイクル特性図である。FIG. 1 is a cycle characteristic diagram of a battery.
【図２】電池のサイクル特性図である。FIG. 2 is a cycle characteristic diagram of a battery.
【図３】活物質に対する混合析出物の重量比率と、電池
容量との関係を表す図である。FIG. 3 is a diagram showing a relationship between a weight ratio of a mixed deposit with respect to an active material and a battery capacity.
Ａ・・・・・本発明電池 Ｘ、Ｙ・・・比較電池 A: Inventive battery X, Y: Comparative battery
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新山 克彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 木本 衛 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiko Niiyama 2-5-5 Keihan Hon-dori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Mamoru Kimoto 2-chome, Keihan-hondori, Moriguchi-shi, Osaka 5-5 Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi City, Osaka Prefecture Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito Keihan Hondori, Moriguchi City, Osaka Prefecture 2-5-5 Sanyo Electric Co., Ltd.
Claims (16)
ンガン及びコバルトを含む混合析出物とからなる活物質
を用いるニッケル極であって、前記粒子が前記混合析出
物にて被覆されたことを特徴とするアルカリ蓄電池用非
焼結式ニッケル極。1. A nickel electrode using an active material comprising particles mainly composed of nickel hydroxide and a mixed precipitate containing manganese and cobalt, wherein the particles are coated with the mixed precipitate. A unique non-sintered nickel electrode for alkaline storage batteries.
対して、２重量％〜26重量％の範囲であることを特徴と
する請求項１記載のアルカリ蓄電池用非焼結式ニッケル
極。2. The non-sintered nickel electrode for an alkaline storage battery according to claim 1, wherein the mixed precipitate is in the range of 2% by weight to 26% by weight with respect to the weight of the active material. .
対して、３重量％〜25重量％の範囲であることを特徴と
する請求項１記載のアルカリ蓄電池用非焼結式ニッケル
極。3. The non-sintered nickel electrode for an alkaline storage battery according to claim 1, wherein the mixed precipitate is in the range of 3% by weight to 25% by weight with respect to the weight of the active material. .
て前記コバルトに対する金属換算量で、0.5重量％〜50
重量％の範囲で添加されたことを特徴とする請求項１記
載のアルカリ蓄電池用非焼結式ニッケル極。4. The manganese is 0.5% by weight to 50% by metal equivalent to the cobalt in the mixed precipitate.
The non-sintered nickel electrode for an alkaline storage battery according to claim 1, wherein the non-sintered nickel electrode is added in a range of wt%.
ンガン及びコバルトを含む混合析出物とからなる活物質
であって、前記粒子が前記混合析出物にて被覆されたこ
とを特徴とするアルカリ蓄電池に用いる非焼結式ニッケ
ル極用活物質。5. An active material comprising particles mainly composed of nickel hydroxide and a mixed precipitate containing manganese and cobalt, wherein the particles are coated with the mixed precipitate. Non-sintered nickel electrode active material used in storage batteries.
対して、２重量％〜26重量％の範囲であることを特徴と
する請求項５記載のアルカリ蓄電池に用いる非焼結式ニ
ッケル極用活物質。6. The non-sintered nickel used in the alkaline storage battery according to claim 5, wherein the mixed precipitate is in the range of 2 wt% to 26 wt% with respect to the weight of the active material. Very active material.
対して、３重量％〜25重量％の範囲であることを特徴と
する請求項５記載のアルカリ蓄電池に用いる非焼結式ニ
ッケル極用活物質。7. The non-sintered nickel used in the alkaline storage battery according to claim 5, wherein the mixed precipitate is in the range of 3% by weight to 25% by weight with respect to the weight of the active material. Very active material.
て前記コバルトに対する金属換算量で、0.5重量％〜50
重量％の範囲で添加されたことを特徴とする請求項５記
載のアルカリ蓄電池に用いる非焼結式ニッケル極用活物
質。8. The manganese is 0.5% by weight to 50% by metal conversion amount with respect to the cobalt in the mixed precipitate.
The non-sintered nickel electrode active material used in the alkaline storage battery according to claim 5, wherein the active material is used in the range of wt%.
ンガン塩溶液とコバルト塩溶液とからなる混合溶液中に
浸漬し、中和を行い、マンガン及びコバルトからなる混
合析出物にて前記粒子を被覆したことを特徴とするアル
カリ蓄電池に用いる非焼結式ニッケル極用活物質の製造
方法。9. Particles containing nickel hydroxide as a main component are immersed in a mixed solution of a manganese salt solution and a cobalt salt solution for neutralization, and the particles are mixed with a mixed precipitate of manganese and cobalt. A method for producing a non-sintered nickel electrode active material for use in an alkaline storage battery, which is characterized by being coated.
に対して、２重量％〜26重量％の範囲であることを特徴
とする請求項９記載のアルカリ蓄電池に用いる非焼結式
ニッケル極用活物質の製造方法。10. The non-sintered nickel used in the alkaline storage battery according to claim 9, wherein the mixed precipitate is in the range of 2 wt% to 26 wt% with respect to the weight of the active material. Method for producing active material for extraordinary use.
に対して、３重量％〜25重量％の範囲であることを特徴
とする請求項９記載のアルカリ蓄電池に用いる非焼結式
ニッケル極用活物質の製造方法。11. The non-sintered nickel used in the alkaline storage battery according to claim 9, wherein the mixed precipitate is in a range of 3 wt% to 25 wt% with respect to the weight of the active material. Method for producing active material for extraordinary use.
いて前記コバルトに対する金属換算量で、0.5重量％〜5
0重量％の範囲で添加されたことを特徴とする請求項９
記載のアルカリ蓄電池に用いる非焼結式ニッケル極用活
物質の製造方法。12. The manganese is 0.5% by weight to 5% by metal conversion amount with respect to the cobalt in the mixed precipitate.
The composition according to claim 9, wherein the content is 0% by weight.
A method for producing a non-sintered nickel electrode active material for use in the alkaline storage battery described above.
マンガン塩溶液とコバルト塩溶液とからなる混合溶液中
に浸漬し、中和を行い、マンガン及びコバルトからなる
混合析出物にて前記粒子を被覆した活物質を得、 この活物質を導電芯体に充填することを特徴とするアル
カリ蓄電池用非焼結式ニッケル極の製造方法。13. Particles comprising nickel hydroxide as a main component,
Immersion in a mixed solution consisting of a manganese salt solution and a cobalt salt solution, neutralization, to obtain an active material in which the particles are coated with a mixed precipitate of manganese and cobalt, and this active material is used as a conductive core. A method for producing a non-sintered nickel electrode for an alkaline storage battery, which is characterized by filling.
に対して、２重量％〜26重量％の範囲であることを特徴
とする請求項１３記載のアルカリ蓄電池用非焼結式ニッ
ケル極の製造方法。14. The non-sintered nickel electrode for an alkaline storage battery according to claim 13, wherein the mixed precipitate is in the range of 2 wt% to 26 wt% with respect to the weight of the active material. Manufacturing method.
に対して、３重量％〜25重量％の範囲であることを特徴
とする請求項１３記載のアルカリ蓄電池用非焼結式ニッ
ケル極の製造方法。15. The non-sintered nickel electrode for an alkaline storage battery according to claim 13, wherein the mixed precipitate is in the range of 3% by weight to 25% by weight with respect to the weight of the active material. Manufacturing method.
いて前記コバルトに対する金属換算量で、0.5重量％〜5
0重量％の範囲で添加されたことを特徴とする請求項１
３記載のアルカリ蓄電池用非焼結式ニッケル極の製造方
法。16. The manganese is 0.5% by weight to 5% by metal conversion amount with respect to the cobalt in the mixed precipitate.
2. The composition was added in the range of 0% by weight.
4. The method for producing a non-sintered nickel electrode for an alkaline storage battery according to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04567595A JP3253476B2 (en) | 1995-03-06 | 1995-03-06 | Non-sintered nickel electrode for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04567595A JP3253476B2 (en) | 1995-03-06 | 1995-03-06 | Non-sintered nickel electrode for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08241713A true JPH08241713A (en) | 1996-09-17 |
| JP3253476B2 JP3253476B2 (en) | 2002-02-04 |
Family
ID=12725975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04567595A Expired - Lifetime JP3253476B2 (en) | 1995-03-06 | 1995-03-06 | Non-sintered nickel electrode for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3253476B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2748607A1 (en) * | 1996-05-07 | 1997-11-14 | Accumulateurs Fixes | PICK-UP NICKEL ELECTRODE FOR AN ALKALINE BATTERY |
| JPH10275631A (en) * | 1996-12-27 | 1998-10-13 | Canon Inc | Powder material, electrode structure, manufacture of them, and secondary battery |
| EP0967673A3 (en) * | 1998-06-15 | 2001-10-10 | Matsushita Electric Industrial Co., Ltd. | Cathode active material for alkaline storage battery and cathode using the same |
| JP2005251755A (en) * | 1996-12-27 | 2005-09-15 | Canon Inc | Powder material, electrode structure, manufacturing method of powder material and electrode structure, and secondary battery |
-
1995
- 1995-03-06 JP JP04567595A patent/JP3253476B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2748607A1 (en) * | 1996-05-07 | 1997-11-14 | Accumulateurs Fixes | PICK-UP NICKEL ELECTRODE FOR AN ALKALINE BATTERY |
| JPH10275631A (en) * | 1996-12-27 | 1998-10-13 | Canon Inc | Powder material, electrode structure, manufacture of them, and secondary battery |
| JP2005251755A (en) * | 1996-12-27 | 2005-09-15 | Canon Inc | Powder material, electrode structure, manufacturing method of powder material and electrode structure, and secondary battery |
| JP4533216B2 (en) * | 1996-12-27 | 2010-09-01 | キヤノン株式会社 | Powder material, electrode structure, manufacturing method thereof, and secondary battery |
| EP0967673A3 (en) * | 1998-06-15 | 2001-10-10 | Matsushita Electric Industrial Co., Ltd. | Cathode active material for alkaline storage battery and cathode using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3253476B2 (en) | 2002-02-04 |
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