JP2001291515A - Nickel hydroxide powder for alkaline secondary battery and its manufacturing method and evaluation method - Google Patents
Nickel hydroxide powder for alkaline secondary battery and its manufacturing method and evaluation methodInfo
- Publication number
- JP2001291515A JP2001291515A JP2000108435A JP2000108435A JP2001291515A JP 2001291515 A JP2001291515 A JP 2001291515A JP 2000108435 A JP2000108435 A JP 2000108435A JP 2000108435 A JP2000108435 A JP 2000108435A JP 2001291515 A JP2001291515 A JP 2001291515A
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- Japan
- Prior art keywords
- hydroxide
- cobalt
- nickel hydroxide
- nickel
- powder
- 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.)
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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
Landscapes
- Analysing Materials By The Use Of Radiation (AREA)
- Sampling And Sample Adjustment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非焼結式アルカリ
二次電池の正極用活物質として好適で、高充填密度を有
し、水酸化コバルトを被覆した水酸化ニッケル粉末とそ
の製造方法および評価方法に関する。The present invention relates to a nickel hydroxide powder which is suitable as a positive electrode active material of a non-sintered alkaline secondary battery, has a high packing density, and is coated with cobalt hydroxide, a method for producing the same, and Regarding the evaluation method.
【０００２】[0002]
【従来の技術】ポータブルエレクトロニクス機器の小型
軽量化により、その電源である電池においては、高エネ
ルギー密度化が要求されている。このために、９５％の
高多孔度の金属繊維焼結体を電極基板とし、活物質とし
て水酸化ニッケル粉末をペースト状にして充填するペー
スト式ニッケル極板が開発されている。2. Description of the Related Art As portable electronic devices have become smaller and lighter, batteries as a power source have been required to have higher energy density. To this end, a paste-type nickel electrode plate has been developed in which a metal fiber sintered body having a high porosity of 95% is used as an electrode substrate and nickel hydroxide powder is filled in a paste form as an active material.
【０００３】このような使用においては、活物質である
水酸化ニッケルを高密度に充填できるという利点と引き
換えに、活物質利用率、ひいては電極利用率が低下する
という問題があった。[0003] In such a use, there is a problem that the active material utilization rate and, consequently, the electrode utilization rate are lowered in exchange for the advantage that nickel hydroxide as an active material can be filled at a high density.
【０００４】活物質利用率を向上させるためには、電極
基板と活物質である水酸化ニッケル粒子との間の導電性
を高める必要がある。このため、水酸化ニッケル粉末の
ぺ一スト作製時に、水酸化コバルト等のコバルト化合物
を混合添加し、電極反応により高導電性のオキシ水酸化
コバルトとし、電極基板と水酸化ニッケル粒子間の導電
性を改善することが一般的である。[0004] In order to improve the utilization rate of the active material, it is necessary to increase the conductivity between the electrode substrate and the nickel hydroxide particles as the active material. For this reason, at the time of producing the nickel hydroxide powder paste, a cobalt compound such as cobalt hydroxide is mixed and added, and a highly conductive cobalt oxyhydroxide is formed by an electrode reaction. Is generally improved.
【０００５】しかし、コバルト化合物を水酸化ニッケル
粉末に混合する方法では、均一に分散することが困難で
あり、少量のコバルト化合物の添加では、導電性の改善
は望めない。従って、充填密度の低いコバルト化合物粉
末を１０％程度混合する必要があり、結果として、活物
質である水酸化ニッケル粒子自体の充填量を低下させて
しまうという問題が新たに生じる。[0005] However, it is difficult to uniformly disperse the cobalt compound in the nickel hydroxide powder by the method of mixing it, and the addition of a small amount of the cobalt compound cannot improve the conductivity. Therefore, it is necessary to mix about 10% of a cobalt compound powder having a low filling density, and as a result, a new problem arises in that the filling amount of the nickel hydroxide particles as the active material itself is reduced.
【０００６】そのため、水酸化ニッケル表面に、種々の
コバルト化合物を被覆する方法が考えられている。たと
えば、特開平３−９３１６１号公報に開示されるよう
に、無電解メッキ等を用いて水酸化ニッケル表面にコバ
ルトを被覆する方法、あるいは特開平６−１８７９８４
号公報に開示されるように、メカノケミカル反応によっ
てコバルト等を表面に被覆する方法がある。Therefore, a method of coating various nickel compounds on the surface of nickel hydroxide has been considered. For example, as disclosed in JP-A-3-93161, a method of coating the surface of nickel hydroxide with cobalt using electroless plating or the like, or JP-A-6-187984.
As disclosed in Japanese Unexamined Patent Publication, there is a method of coating the surface with cobalt or the like by a mechanochemical reaction.
【０００７】特に、水酸化ニッケル粒子の表面に水酸化
コバルトを被覆する方法としては、例えば特開平７−１
３３１１５号公報には、高タッピング密度の水酸化ニッ
ケル粒子を水に分散させ、これに硫酸コバルト水溶液と
アンモニア水とを同時に添加して、その反応系を水酸化
ナトリウム水溶液でｐＨ１１〜１３の範囲にコントロー
ルしながら、水酸化ニッケル粒子の表面に、水酸化コバ
ルト被覆層を形成させる方法が記載されている。これは
アンモニウムイオンを反応系に存在させて、コバルト塩
の溶解度を高めることにより、均一な水酸化コバルト層
の形成を目的としている。In particular, as a method for coating the surface of nickel hydroxide particles with cobalt hydroxide, for example, Japanese Patent Application Laid-Open No.
No. 33115 discloses that nickel hydroxide particles having a high tapping density are dispersed in water, an aqueous solution of cobalt sulfate and aqueous ammonia are simultaneously added thereto, and the reaction system is adjusted to pH 11 to 13 with an aqueous solution of sodium hydroxide. It describes a method of forming a cobalt hydroxide coating layer on the surface of nickel hydroxide particles while controlling. This aims at forming a uniform cobalt hydroxide layer by increasing the solubility of the cobalt salt by causing ammonium ions to be present in the reaction system.
【０００８】しかしながら、該公報の実施例に示される
ように、水酸化コバルト被覆粒子のタッピング密度が、
核となる水酸化ニッケル粒子の密度に比べて０．２ｇ／
ｍｌ以上も低下しており、目的とした高密度充填に対し
て十分とは言えない。However, as shown in the examples of the publication, the tapping density of the cobalt hydroxide-coated particles is
0.2 g / density compared to the density of nickel hydroxide particles
ml, which is not sufficient for the intended high-density filling.
【０００９】上記タッピング密度の低下の要因は、被覆
層である水酸化コバルトの結晶性の問題により、密度の
低い被覆層が形成されることにある。その結果として、
水酸化コバルト被覆粒子の低密度化という問題が生じ
る。[0009] The cause of the decrease in the tapping density is that a coating layer having a low density is formed due to the crystallinity problem of the cobalt hydroxide serving as the coating layer. As a result,
There is a problem that the density of the cobalt hydroxide-coated particles is reduced.
【００１０】[0010]
【発明が解決しようとする課題】上記問題を解決するた
め、本発明は、ペースト法でアルカリ二次電池の正極を
製造するのに適し、水酸化コバルト被覆層を有する水酸
化ニッケル粉末とその製造方法を提供することを課題と
する。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention relates to a nickel hydroxide powder having a cobalt hydroxide coating layer, which is suitable for producing a cathode of an alkaline secondary battery by a paste method, and a method for producing the same. It is an object to provide a method.
【００１１】また、本発明は、上記した水酸化ニッケル
粉末の製造に当たって、被覆層である水酸化コバルトの
結晶性の評価方法を提供することを課題とする。有効な
評価方法を提供することにより、被覆層である水酸化コ
バルトの結晶性の良否判定が可能となるため、緻密で、
結晶性の良い、高いタップ密度を有するアルカリ二次電
池用水酸化ニッケル粉末の製造の一助となる。また同時
に、アルカリ二次電池に組み込んでから容量を測ること
なしに、迅速な活物質評価も可能となる。Another object of the present invention is to provide a method for evaluating the crystallinity of a coating layer of cobalt hydroxide in producing the above-mentioned nickel hydroxide powder. By providing an effective evaluation method, it is possible to determine the quality of the crystallinity of the cobalt hydroxide coating layer, dense,
This helps to produce nickel hydroxide powder for alkaline secondary batteries having good crystallinity and high tap density. At the same time, it is possible to quickly evaluate the active material without measuring the capacity after being incorporated into the alkaline secondary battery.
【００１２】[0012]
【課題を解決するための手段】本発明によるアルカリ二
次電池用水酸化ニッケル粉末は、Ｘ線回折において、
（１０１）面より求めた半価幅が０．２２９°以上０．
８５１°以下、あるいは（１０１）面より求めた結晶子
径が１００Å以上４５０Å以下であるβ型水酸化コバル
トにより、表面が被覆されていることを特徴とする。The nickel hydroxide powder for an alkaline secondary battery according to the present invention is characterized in that
The half width obtained from the (101) plane is 0.229 ° or more.
The surface is coated with β-type cobalt hydroxide having a crystallite size of 85 ° or less or a crystallite diameter determined from the (101) plane of 100 ° or more and 450 ° or less.
【００１３】本発明による水酸化コバルト被覆層を有す
る水酸化ニッケル粉末の製造方法は、次のようになる。A method for producing a nickel hydroxide powder having a cobalt hydroxide coating layer according to the present invention is as follows.
【００１４】水酸化ニッケル反応槽に、ニッケル水溶液
とアンモニウムイオン供給体とを連続的に供給してろ液
とし、該ろ液中のニッケルイオン濃度が５〜８ｍｇ／リ
ットルになるように、ｐＨコントローラと連動させてｐ
Ｈを１１〜１３に維持し、槽内温度５０±１℃に保持し
つつ、アルカリ金属水酸化物水溶液を添加することによ
り、球状水酸化ニッケルを生成し、前記球状水酸化ニッ
ケルを、スラリーごとオーバーフローさせ、水酸化コバ
ルト被覆層反応槽に連続して受け入れ、コバルト水溶液
とアンモニウムイオン供給体と不活性ガスを、充分に攪
拌された該水酸化コバルト被覆層反応槽に連続して供給
してろ液とし、該ろ液中のコバルトイオン濃度が３〜６
ｍｇ／リットルになるように、ｐＨコントローラと連動
させてｐＨを１１〜１３に維持し、槽内温度を５０±１
℃に保持しつつ、アルカリ金属水酸化物水溶液を添加す
ることにより、前記球状水酸化ニッケルの表面に、水酸
化コバルト被覆層を生成させる。A nickel aqueous solution and an ammonium ion supplier are continuously supplied to a nickel hydroxide reaction tank to form a filtrate, and a pH controller and a pH controller are set so that the nickel ion concentration in the filtrate is 5 to 8 mg / liter. In conjunction with p
While maintaining H at 11 to 13 and maintaining the inside temperature of the tank at 50 ± 1 ° C., an aqueous alkali metal hydroxide solution is added to generate spherical nickel hydroxide, and the spherical nickel hydroxide is mixed with the slurry. Overflow, continuously receive in the cobalt hydroxide coating layer reactor, continuously supply the aqueous cobalt solution, ammonium ion supplier and inert gas to the well-stirred cobalt hydroxide coating layer reactor and filtrate And the cobalt ion concentration in the filtrate is 3-6.
The pH is maintained at 11 to 13 in conjunction with a pH controller so that the concentration becomes mg / liter, and the temperature in the bath is set to 50 ± 1.
By adding an aqueous solution of an alkali metal hydroxide while maintaining the temperature at ° C., a cobalt hydroxide coating layer is formed on the surface of the spherical nickel hydroxide.
【００１５】本発明によるアルカリ二次電池用水酸化ニ
ッケル粉末の評価方法は、有機溶剤中に、水酸化コバル
ト被覆層を有する水酸化ニッケル粉末を浸漬し、攪拌混
合し縣濁させた後、水酸化コバルトを主とする縣濁部
と、水酸化ニッケルを主とする沈澱部とを、デカンテー
ション操作により分離し、前記縣濁部より水酸化コバル
トを濾別回収した後、該回収物の粉体特性を評価する。The method for evaluating nickel hydroxide powder for an alkaline secondary battery according to the present invention is as follows. A nickel hydroxide powder having a cobalt hydroxide coating layer is immersed in an organic solvent, stirred, mixed and suspended. The suspension mainly containing cobalt and the precipitation mainly containing nickel hydroxide are separated by a decantation operation, and the cobalt hydroxide is collected by filtration from the suspension, and then the powder of the recovered material is obtained. Evaluate the properties.
【００１６】有機溶剤としては、溶解性パラメーターが
１２以下のアルコールが使用できる。As the organic solvent, an alcohol having a solubility parameter of 12 or less can be used.
【００１７】濾過後の乾燥時間を考慮するとイソプロピ
ルアルコール、ブタノール等が望ましい。Considering the drying time after filtration, isopropyl alcohol, butanol and the like are preferable.
【００１８】上記により回収した水酸化コバルトの粉体
特性は、Ｘ線回折において（１０１）面の半価幅または
結晶子径を測定する。評価は、例えば（１０１）面であ
れば、半価幅が０．２２９°以上０．８５１°以下であ
ればよく、あるいは結晶子径が１００Å以上４５０Å以
下であればよい。The powder properties of the cobalt hydroxide recovered as described above are determined by measuring the half width or crystallite diameter of the (101) plane by X-ray diffraction. For example, in the case of the (101) plane, the half width may be 0.229 ° or more and 0.851 ° or less, or the crystallite diameter may be 100 ° or more and 450 ° or less.
【００１９】評価方法として、電極利用率を使用する。
電極利用率は、理論容量に対する放電容量の比率で表さ
れる。As an evaluation method, an electrode utilization factor is used.
The electrode utilization is represented by the ratio of the discharge capacity to the theoretical capacity.
【００２０】[0020]
【発明の実施の形態】本発明による水酸化コバルトを被
覆した水酸化ニッケル粉末は、被覆層を形成する水酸化
コバルトの粉体特性が、Ｘ線回折（ＸＲＤ）において
（１０１）面の回折線より求めた半価幅が０．２２９°
以上０．８５１°以下、あるいは結晶子径が１００Å以
上４５０Å以下である。BEST MODE FOR CARRYING OUT THE INVENTION In the nickel hydroxide powder coated with cobalt hydroxide according to the present invention, the powder property of the cobalt hydroxide forming the coating layer is determined by X-ray diffraction (XRD) of diffraction line of (101) plane. The half width obtained from the calculation is 0.229 °
0.851 ° or less, or the crystallite diameter is 100 ° or more and 450 ° or less.
【００２１】表面被覆層の水酸化コバルトの（１０１）
面の回折線から求めた半価幅が０．２２９°未満の場
合、また、結晶子径が１００Å未満の場合には、空気酸
化により容易に酸化されるため、アルカリ二次電池作製
時に水酸化ニッケルの電極利用率が低下してしまう。The surface coating layer of cobalt hydroxide (101)
When the half-value width determined from the diffraction line of the plane is less than 0.229 ° or when the crystallite diameter is less than 100 °, it is easily oxidized by air oxidation. The electrode utilization of nickel decreases.
【００２２】また、半価幅が０．８５１°を超えた場
合、また、結晶子径が４５０Åを超えた場合には、被覆
層の水酸化コバルトがアルカリ電解液中に十分に溶解せ
ず、電極利用率が低下する。When the half width exceeds 0.851 °, or when the crystallite diameter exceeds 450 °, cobalt hydroxide in the coating layer is not sufficiently dissolved in the alkaline electrolyte. Electrode utilization decreases.
【００２３】ＸＲＤは、たとえばサンプリング幅０．０
２°、走査速度４°／ｍｉｎで２θ＝３５°〜４１°の
範囲で行い、得られた回折データよりバックグランドを
除いた後、ピーク強度が半分となる回折線の拡がりから
半価幅を求める。得られた半価幅からシェラーの式 Ｄ＝０．９λ／（β・ｃｏｓθ） により結晶子径を求めた。ここで、Ｄは結晶子径
［Å］、λはＸ線の波長［Å］、βは結晶の大きさによ
る回折ピークの拡がり［ｒａｄ］、θは回折角［ｄｅ
ｇ］であり、βと半価幅（ｂ）の関係は、ガウス型近似
によれば β2＝ｂ2−ｂ0 2 となる。ただし、ｂ0は装置による拡がり誤差である。XRD is, for example, a sampling width of 0.0
The scan was performed at 2 ° and a scan speed of 4 ° / min in the range of 2θ = 35 ° to 41 °, and after removing the background from the obtained diffraction data, the half-value width was calculated from the spread of the diffraction line at which the peak intensity became half. Ask. The crystallite diameter was determined from the obtained half width according to Scherrer's formula D = 0.9λ / (β · cos θ). Here, D is the crystallite diameter [Å], λ is the X-ray wavelength [Å], β is the spread of the diffraction peak depending on the crystal size [rad], and θ is the diffraction angle [de].
a g], the relationship of beta and the half width (b) is a β 2 = b 2 -b 0 2 According to the Gaussian approximation. Here, b 0 is a spreading error caused by the device.
【００２４】（製造方法）水酸化コバルト被覆層を有す
る水酸化ニッケル粉末は、例えば以下の方法で作製が可
能である。(Production Method) The nickel hydroxide powder having a cobalt hydroxide coating layer can be produced, for example, by the following method.
【００２５】（第１の方法）原料である高嵩密度水酸化
ニッケルを、たとえば特開平９−０１７４２９号公報に
あげる方法で製造し、該高嵩密度水酸化ニッケル（タッ
プ密度２．１７ｇ／ｍｌ）５ｋｇを、５０℃に保持した
１９リットルの純水と１．１リットルのアンモニア水
（２５％ＮＨ3）の混合液中に懸濁させるか、あるいは
５０℃に保持した２０リットルの純水中に懸濁させ、攪
拌しつつ、上記方法（特開平７−１３３１１５号公報）
で調整した硫酸コバルト水溶液と、アンモニア水を同時
添加しつつ、苛性ソーダ溶液でｐＨを１２．０にコント
ロールする。硫酸コバルト水溶液の添加速度は、３２ｍ
ｌ／ｍｉｎ、アンモニア水の添加速度は、４．７ｍｌ／
ｍｉｎとする。添加は、窒素ガスを７リットル／ｍｉｎ
でパージし、コバルト含有率が計算上３％となる時間
（５０ｍｉｎ）行う。反応終了後、生成した沈殿物を直
ちにブフナーロートで吸引濾過し、１０リットルの純水
で２回レパルプ水洗後、濾過乾燥して、水酸化コバルト
被覆層を有する水酸化ニッケル粉末を得る。なお、水酸
化コバルトの被覆量は反応時間により制御が可能であ
る。(First Method) A high bulk density nickel hydroxide as a raw material is produced, for example, by the method described in JP-A-9-017429, and the high bulk density nickel hydroxide (tap density 2.17 g / ml) is produced. 5) suspend 5 kg in a mixture of 19 liters of pure water kept at 50 ° C. and 1.1 liters of ammonia water (25% NH 3 ), or 20 liters of pure water kept at 50 ° C. The above method (Japanese Patent Application Laid-Open No. 7-133115)
The pH is controlled to 12.0 with a sodium hydroxide solution while simultaneously adding the aqueous solution of cobalt sulfate and the aqueous ammonia adjusted in the above. The addition speed of the aqueous solution of cobalt sulfate is 32 m
l / min, the addition rate of ammonia water is 4.7 ml /
min. Addition of nitrogen gas at 7 liter / min
And the time (50 min) when the cobalt content becomes 3% in calculation. After the completion of the reaction, the resulting precipitate is immediately suction-filtered with a Buchner funnel, washed twice with 10 l of pure water and then dried by filtration to obtain a nickel hydroxide powder having a cobalt hydroxide coating layer. The coating amount of cobalt hydroxide can be controlled by the reaction time.
【００２６】（第２の方法）第２の方法に用いる装置
を、図１に例示する。(Second Method) FIG. 1 illustrates an apparatus used in the second method.
【００２７】原料である高嵩密度水酸化ニッケルを、た
とえば特開平９−０１７４２９号公報にあげる方法で製
造する。A high bulk density nickel hydroxide as a raw material is produced, for example, by the method described in JP-A-9-017429.
【００２８】先ず、水酸化ニッケル反応槽１に、ニッケ
ル塩化水溶液供給ライン２によりニッケルを含む水溶液
を、アンモニウムイオン供給ライン３によりアンモニア
水を、アルカリ金属水酸化物水溶液供給ライン４から水
酸化アルカリ水溶液を、それぞれ連続的に供給し、水酸
化ニッケルスラリーを生成させる。First, an aqueous solution containing nickel is supplied to a nickel hydroxide reaction tank 1 through a nickel chloride aqueous solution supply line 2, ammonia water is supplied through an ammonium ion supply line 3, and an alkali hydroxide aqueous solution is supplied through an alkali metal hydroxide aqueous solution supply line 4. Are continuously supplied to generate a nickel hydroxide slurry.
【００２９】次に、水酸化ニッケル反応槽１より、オー
バーフロー（オーバーフローライン１１）で取り出した
水酸化ニッケルスラリーを、ろ過、水洗、乾燥すること
無く、そのままで水酸化コバルト被覆層反応槽１２で受
ける。その水酸化コバルト被覆層反応槽１２に、コバル
ト塩水溶液（コバルト塩水溶液供給ライン１３により供
給）、アンモニウムイオン供給体（アンモニウムイオン
供給ライン１４により供給）を連続的に供給し、攪拌機
１０により攪拌する。Next, the nickel hydroxide slurry taken out from the nickel hydroxide reaction tank 1 through the overflow (overflow line 11) is received as it is in the cobalt hydroxide coating layer reaction tank 12 without being filtered, washed and dried. . A cobalt salt aqueous solution (supplied by a cobalt salt aqueous solution supply line 13) and an ammonium ion supplier (supplied by an ammonium ion supply line 14) are continuously supplied to the cobalt hydroxide coating layer reaction tank 12, and the mixture is stirred by the stirrer 10. .
【００３０】この際、定量ポンプ７と、水酸化コバルト
被覆層反応槽１２内にｐＨセンサ５を配置したｐＨコン
トローラ６とを連動させて、アルカリ金属水酸化物水溶
液供給ライン４から、槽内のｐＨを１１〜１３に維持し
つつ、アルカリ金属水酸化物水溶液または酸類を供給す
る。さらに、温度センサ８と、図示しない加熱装置とを
連動させて槽内温度５０±１℃に保持する。槽内の雰囲
気は、不活性ガス供給ライン１５から供給する不活性ガ
スとする。At this time, the metering pump 7 and the pH controller 6 in which the pH sensor 5 is disposed in the cobalt hydroxide coating layer reaction tank 12 are linked to each other, and the alkali metal hydroxide aqueous solution supply line 4 supplies While maintaining the pH at 11 to 13, an aqueous alkali metal hydroxide solution or acids are supplied. Further, the temperature sensor 8 and a heating device (not shown) are linked to maintain the temperature in the bath at 50 ± 1 ° C. The atmosphere in the tank is an inert gas supplied from the inert gas supply line 15.
【００３１】水酸化コバルトを表面にコートした水酸化
ニッケルを、水酸化コバルト被覆層反応槽１２より、オ
ーバーフロー（水酸化コバルトコートオーバーフローラ
イン１６）で連続的に取り出す。これをろ過、水洗、乾
燥し、水酸化コバルト被覆層を有する水酸化ニッケル粉
末を得る。The nickel hydroxide coated on the surface with cobalt hydroxide is continuously taken out from the cobalt hydroxide coating layer reaction tank 12 by overflow (cobalt hydroxide coat overflow line 16). This is filtered, washed with water, and dried to obtain a nickel hydroxide powder having a cobalt hydroxide coating layer.
【００３２】この第２の方法によれば、水酸化コバルト
被覆層製造反応工程で、ｐＨ緩衝性のある母液をそのま
ま使用可能であり、また、供給するアンモニウムイオン
供給体、およびコバルトの酸化を防止するための窒素ガ
スが削減でき、かつ、工程を連続化することにより、生
産性、品質安定性が向上できる。According to the second method, the mother liquor having a pH buffer property can be used as it is in the reaction step for producing the cobalt hydroxide coating layer, and the supplied ammonium ion donor and the oxidation of cobalt are prevented. By reducing the amount of nitrogen gas required for the process, and by making the process continuous, productivity and quality stability can be improved.
【００３３】また、水酸化コバルトにはα型とβ型が存
在するが、本発明の被覆層となる水酸化コバルトは、ｐ
Ｈ１１以上の高アルカリ溶液中で生成するため、通常、
β型水酸化コバルトである。逆説的には、β型水酸化コ
バルトでなければ、（１０１）面にＸＲＤによる回折線
は現れず、本発明による判定、評価は困難である。There are α-type and β-type in cobalt hydroxide. Cobalt hydroxide used as the coating layer of the present invention is p-type.
Since it is produced in a highly alkaline solution of H11 or more, usually,
β-type cobalt hydroxide. Paradoxically, unless it is β-type cobalt hydroxide, no diffraction line by XRD appears on the (101) plane, and it is difficult to determine and evaluate according to the present invention.
【００３４】（評価方法）本発明による水酸化コバルト
被覆層を有する水酸化ニッケル粉末の評価方法は、以下
のようである。(Evaluation Method) The evaluation method of the nickel hydroxide powder having the cobalt hydroxide coating layer according to the present invention is as follows.
【００３５】有機溶剤中に、水酸化コバルト被覆層を有
する水酸化ニッケル粉末を浸漬し、攪拌混合する。この
際に、水酸化ニッケル粒子表面の被覆された水酸化コバ
ルトは、水酸化ニッケル粒子との相互作用が変化するた
めに剥がれて、溶媒中に分散し、懸濁する。A nickel hydroxide powder having a cobalt hydroxide coating layer is immersed in an organic solvent and mixed with stirring. At this time, the cobalt hydroxide coated on the surface of the nickel hydroxide particles is peeled off due to a change in the interaction with the nickel hydroxide particles, and is dispersed and suspended in the solvent.
【００３６】これは、ＤＬＢ理論によれば、水系溶媒中
でヘテロ凝集状態にあった球状水酸化ニッケル粒子と水
酸化コバルト微粒子が、非水系の溶媒中で表面電位が変
化するために、相互作用が引力から斥力に代わるためで
あると考えられる。According to the DLB theory, the interaction between spherical nickel hydroxide particles and cobalt hydroxide fine particles which were in a hetero-aggregated state in an aqueous solvent changes due to a change in surface potential in a non-aqueous solvent. Is considered to be due to the repulsive force replacing the attractive force.
【００３７】水酸化コバルトを主とする懸濁部と、水酸
化ニッケルを主とする沈澱部を、デカンテーション操作
により分離し、前記懸濁部より水酸化コバルトを濾別回
収した後、前記被覆層である回収物の粉体特性を評価す
る。The suspended part mainly composed of cobalt hydroxide and the precipitated part mainly composed of nickel hydroxide are separated by a decantation operation. Evaluate the powder properties of the collected material as a layer.
【００３８】攪拌混合時は、通常の攪拌混合操作である
攪拌子とマグネティクスターラーによるもの、あるいは
攪拌羽根とモーターによるもので十分である。また、超
音波洗浄機構付き等の分散機であれば、さらに効率よ
く、短時間で処理が可能である。At the time of stirring and mixing, a normal stirring and mixing operation using a stirrer and a magnetic stirrer, or using a stirring blade and a motor is sufficient. Further, if a dispersing machine having an ultrasonic cleaning mechanism is used, the processing can be performed more efficiently in a short time.
【００３９】分離溶媒として用いる有機溶剤としては、
溶解性パラメーターが１２以下のアルコールがよい。た
とえば、溶解性パラメータが１２．９２のエタノールで
は、水の溶解性パラメーター（２３．５）と比較して変
化量が小さいため、分離溶媒として用いた場合、粒子表
面電位の変化が小さく、結果として粒子間相互作用によ
る引力が斥力に変化しないために、水酸化コバルト被覆
層が剥がれない。As the organic solvent used as the separation solvent,
Alcohols having a solubility parameter of 12 or less are preferred. For example, in ethanol having a solubility parameter of 12.92, the amount of change is small as compared with the solubility parameter of water (23.5). Therefore, when used as a separation solvent, the change in particle surface potential is small. Since the attractive force due to the interaction between particles does not change into a repulsive force, the cobalt hydroxide coating layer does not peel off.
【００４０】溶解性パラメータが水と比較して十分に小
さいものであれば、分離溶媒として使用が可能である
が、操作性を考慮するとアルコールが望ましい。特に炭
素数が小さいイソプロピルアルコール、ブタノール等で
あれば、濾過後の乾燥時間が短縮されるので、より好適
である。If the solubility parameter is sufficiently small as compared with that of water, it can be used as a separation solvent, but alcohol is desirable in view of operability. In particular, isopropyl alcohol, butanol or the like having a small carbon number is more preferable because the drying time after filtration is reduced.
【００４１】水系でｐＨを変化させることによっても、
表面電位を変化させることが可能であるが、この場合
は、水酸化コバルトの結晶状態が変化するので好ましく
ない。By changing the pH in an aqueous system,
Although it is possible to change the surface potential, this is not preferable because the crystal state of cobalt hydroxide changes.
【００４２】上記のように回収した水酸化コバルトの粉
体特性を、前記したように、ＸＲＤにおいて（１０１）
面の半価幅または結晶子径を測定すれば良い。あるい
は、ＸＲＤにおいて（２０２）面の結晶子径を測定し判
定することも可能であるが、（１０１）面での測定に比
較してピーク強度が小さいため、強力なＸ線が必要とな
ったり、積算のために長時間を要するため好ましい方法
ではない。As described above, the powder characteristics of the cobalt hydroxide recovered as described above were determined by XRD using (101)
What is necessary is just to measure the half width or the crystallite diameter of the plane. Alternatively, it is possible to determine the crystallite diameter of the (202) plane by XRD, but it is necessary to use strong X-rays because the peak intensity is smaller than that of the measurement on the (101) plane. This is not a preferable method because it takes a long time for integration.
【００４３】以下、実施例に基づき、本発明の評価方法
をさらに詳しく述べる。Hereinafter, the evaluation method of the present invention will be described in more detail based on examples.
【００４４】（実施例） （実施例１）前記第１の方法で作成した水酸化コバルト
被覆層を有する水酸化ニッケル粉末（被覆量Ｃｏ５ｗｔ
％；タップ密度２．１８ｇ／cc）１００ｇを、５００cc
のビーカに秤り取り、３００ｍｌの２−ブタノールを加
え、超音波洗浄器で１０分間分散させる。３分間静置
後、分散部をデカンテーションにより沈澱部と分離す
る。はく離した水酸化コバルトが縣濁している分散部
を、桐山ロートで吸引濾過し、水酸化コバルトを回収
し、さらに６０℃で乾燥を行う。得られた水酸化コバル
トにおいて、ＸＲＤにより半価幅および結晶子径を求め
た。得られた結果を表１に示す。(Example) (Example 1) Nickel hydroxide powder having a cobalt hydroxide coating layer formed by the first method (coating amount Co5 wt
%; Tap density 2.18 g / cc) 100 g to 500 cc
Weighed into a beaker, and added 300 ml of 2-butanol and dispersed with an ultrasonic cleaner for 10 minutes. After standing for 3 minutes, the dispersion part is separated from the precipitate part by decantation. The dispersed portion in which the separated cobalt hydroxide is suspended is suction-filtered with a Kiriyama funnel to recover the cobalt hydroxide, and further dried at 60 ° C. The half-width and the crystallite diameter of the obtained cobalt hydroxide were determined by XRD. Table 1 shows the obtained results.
【００４５】（実施例２）前記第１の方法で作成した水
酸化コバルト被覆層を有する水酸化ニッケル粉末（被覆
量Ｃｏ３．９ｗｔ％；タップ密度２．１５ｇ／cc）１０
０ｇを、５００ccのビーカに秤り取り、３００ｍｌのイ
ソプロピルアルコールを加え、その後は実施例１と同様
に処理を行った。得られた結果を表１に示す。Example 2 Nickel hydroxide powder having a cobalt hydroxide coating layer formed by the first method (coating amount: 3.9 wt%; tap density: 2.15 g / cc) 10
0 g was weighed and placed in a 500 cc beaker, and 300 ml of isopropyl alcohol was added. Thereafter, the same treatment as in Example 1 was performed. Table 1 shows the obtained results.
【００４６】（実施例３）図１に示す装置で、連続的に
水酸化コバルト被覆層を有する水酸化ニッケル粉末を製
造した。Example 3 A nickel hydroxide powder having a continuous cobalt hydroxide coating layer was produced using the apparatus shown in FIG.
【００４７】図１において、水酸化ニッケル反応槽１
は、３枚の邪魔板を有する１００リットルのタンクであ
る。ニッケル水溶液、アンモニウムイオン供給体、アル
カリ金属水酸化物水溶液として、それぞれ濃度４５０ｇ
／リットルの硫酸ニッケル水溶液、濃度２５重量％のア
ンモニア水、濃度２０重量％の水酸化ナトリウム水溶液
を用いた。In FIG. 1, a nickel hydroxide reactor 1
Is a 100 liter tank with three baffles. Nickel aqueous solution, ammonium ion supplier, alkali metal hydroxide aqueous solution, each concentration 450g
Per liter of an aqueous solution of nickel sulfate, an aqueous solution of ammonia having a concentration of 25% by weight, and an aqueous solution of sodium hydroxide having a concentration of 20% by weight.
【００４８】充分に攪拌された水酸化ニッケル反応槽１
に、硫酸ニッケル水溶液を９２０cc／分、アンモニア水
を６．５cc／分の流量で、連続的に供給した。一方、水
酸化ナトリウム水溶液は、水酸化ニッケル反応槽１内の
ろ液中のニッケルイオン濃度が５〜８ｍｇ／リットルに
なるように、ｐＨコントローラ６と連動させて、槽内温
度５０±１℃に保持しつつ添加することにより、球状水
酸化ニッケルを製造する。こうして生成した水酸化ニッ
ケルを、スラリーごとオーバーフローさせ、水酸化コバ
ルト被覆層反応槽１２に連続して受け入れる。A well-stirred nickel hydroxide reactor 1
, And an aqueous solution of ammonia was continuously supplied at a flow rate of 920 cc / min and an aqueous ammonia solution at a flow rate of 6.5 cc / min. On the other hand, the aqueous sodium hydroxide solution is adjusted to a temperature within the tank of 50 ± 1 ° C. in conjunction with the pH controller 6 so that the nickel ion concentration in the filtrate in the nickel hydroxide reaction tank 1 becomes 5 to 8 mg / liter. By adding while maintaining, spherical nickel hydroxide is produced. The nickel hydroxide thus generated overflows together with the slurry and is continuously received in the cobalt hydroxide coating layer reaction tank 12.
【００４９】水酸化コバルト被覆層反応槽１２も、３枚
の邪魔板を有する１００リットルのタンクで、ここでは
１２０ｇ／リットルの硫酸コバルト水溶液を１９０cc／
分、２５重量％のアンモニア水を１．６cc／分、および
被覆層の酸化を防止する目的で、不活性ガスである窒素
を１リットル／分の流量で、充分に攪拌された水酸化コ
バルト被覆層反応槽１２に連続して供給する。一方、水
酸化ナトリウム水溶液は、濃度２０重量％のものを、水
酸化コバルト被覆層反応槽１２内のろ液中のコバルトイ
オン濃度が、３〜６ｍｇ／リットルになるように、ｐＨ
コントローラ６と連動させて、ｐＨを１１〜１３に制御
し、槽内温度を５０±１℃に保持しつつ添加することに
より、球状水酸化ニッケル表面に水酸化コバルト被覆層
を生成させて、連続的に取り出した。The cobalt hydroxide coating layer reaction tank 12 is also a 100 liter tank having three baffles, in which a 120 g / liter cobalt sulfate aqueous solution is supplied at 190 cc / liter.
Cobalt hydroxide coating which was sufficiently stirred at a flow rate of 1.6 cc / min of 25% by weight ammonia water and nitrogen at 1 liter / min to prevent oxidation of the coating layer. It is continuously supplied to the bed reaction tank 12. On the other hand, a sodium hydroxide aqueous solution having a concentration of 20% by weight was adjusted to a pH value such that the cobalt ion concentration in the filtrate in the cobalt hydroxide coating layer reaction tank 12 became 3 to 6 mg / liter.
By controlling the pH to 11 to 13 in conjunction with the controller 6 and adding while keeping the temperature in the tank at 50 ± 1 ° C., a cobalt hydroxide coating layer is formed on the surface of the spherical nickel hydroxide to continuously Was taken out.
【００５０】得られた水酸化コバルト被覆層を有する水
酸化ニッケル粉末（被覆量Ｃｏ４．６ｗｔ％；タップ密
度２．１４ｇ／cc）を、実施例１と同様に２−ブタノー
ルで処理をして、水酸化コバルトを回収した後、ＸＲＤ
を行った。得られた結果を表１に示す。The obtained nickel hydroxide powder having a cobalt hydroxide coating layer (coating amount: 4.6 wt%; tap density: 2.14 g / cc) was treated with 2-butanol in the same manner as in Example 1. After recovering the cobalt hydroxide, XRD
Was done. Table 1 shows the obtained results.
【００５１】（比較例１）水酸化コバルト被覆層を有す
る水酸化ニッケル粉末（被覆量Ｃｏ５ｗｔ％；タップ密
度２．１４ｇ／cc）を、実施例１と同様に２−ブタノー
ルで処理をして、水酸化コバルトを回収した後、ＸＲＤ
を行った。得られた結果を表１に示す。(Comparative Example 1) Nickel hydroxide powder having a cobalt hydroxide coating layer (coating amount: Co 5 wt%; tap density: 2.14 g / cc) was treated with 2-butanol in the same manner as in Example 1. After recovering the cobalt hydroxide, XRD
Was done. Table 1 shows the obtained results.
【００５２】（比較例２）水酸化コバルト被覆層を有す
る水酸化ニッケル粉末（被覆量Ｃｏ４．５ｗｔ％；タッ
プ密度２．０４ｇ／cc）を、実施例１と同様に２−ブタ
ノールで処理をして、水酸化コバルトを回収した後、Ｘ
ＲＤを行った。得られた結果を表１に示す。Comparative Example 2 Nickel hydroxide powder having a cobalt hydroxide coating layer (coating amount: 4.5 wt%; tap density: 2.04 g / cc) was treated with 2-butanol in the same manner as in Example 1. And after collecting cobalt hydroxide, X
RD was performed. Table 1 shows the obtained results.
【００５３】[0053]
【表１】 [Table 1]
【００５４】（電池評価）実施例１〜３および比較例
１、２の水酸化コバルト被覆層を有する水酸化ニッケル
粉末を用いて、以下のように正極を作製した。(Evaluation of Battery) Positive electrodes were prepared as follows using the nickel hydroxide powder having a cobalt hydroxide coating layer of Examples 1 to 3 and Comparative Examples 1 and 2.
【００５５】水酸化コバルト被覆層を有する水酸化ニッ
ケル粉末に、水酸化コバルト（伊勢化学製）を正極中の
Ｃｏ量が６．５ｗｔ％となるように添加し、バインダー
量が２重量％となるようにＨＰＣ（ヒドロキシプロピル
セルロース１０００〜４０００ｃＰ；和光純薬工業製試
薬１級）水溶液を加えて、ノンバブリングニーダー（日
本精工製）を用いてペースト化し、発泡ニッケル（住友
電工製セルメット：多孔度９５％）に充填し、乾燥後、
２ｔｏｎ／ｃｍ2の圧力で静水圧プレスし、正極とし
た。Cobalt hydroxide (manufactured by Ise Chemical Co., Ltd.) is added to the nickel hydroxide powder having the cobalt hydroxide coating layer so that the amount of Co in the positive electrode becomes 6.5 wt%, and the amount of binder becomes 2 wt%. As described above, an aqueous solution of HPC (hydroxypropylcellulose 1000-4000 cP; reagent grade 1 made by Wako Pure Chemical Industries, Ltd.) is added to form a paste using a non-babbling kneader (manufactured by Nippon Seiko), and nickel foam (Sumitomo Denko Celmet: porosity 95) %), And after drying,
It was hydrostatically pressed at a pressure of 2 ton / cm 2 to obtain a positive electrode.
【００５６】負極には、カドミウム電極、セパレータと
してスルホン化ポリオレフィン不織布をそれぞれ用い
た。電解液には、７．２ｍｏｌ／リットルの水酸化カリ
ウム水溶液を用いた。充電は、０．１Ｃで理論容量（２
８９ｍＡ／ｇ）の１５０％まで行い、放電は、０．２Ｃ
で１．０Ｖまで行った。このときの電極利用率は、理論
容量に対する放電容量の百分率で表される。表２に３サ
イクル目の電極利用率を示す。A cadmium electrode was used as a negative electrode, and a sulfonated polyolefin nonwoven fabric was used as a separator. An 7.2 mol / liter potassium hydroxide aqueous solution was used as the electrolyte. Charging is performed at a theoretical capacity of 0.1 C (2
89 mA / g) up to 150% and discharge is 0.2 C
To 1.0V. The electrode utilization at this time is expressed as a percentage of the discharge capacity with respect to the theoretical capacity. Table 2 shows the electrode utilization in the third cycle.
【００５７】[0057]
【表２】 [Table 2]
【００５８】比較例１では、被覆している水酸化コバル
トの結晶子径が大きいことにより、溶解性に劣り、十分
な導電性ネットワークが形成されないため、電極利用率
が低下している。In Comparative Example 1, the solubility of the cobalt hydroxide was large due to the large crystallite diameter of the coated cobalt hydroxide, and a sufficient conductive network was not formed.
【００５９】比較例２では、被覆している水酸化コバル
トの結晶子径が小さいため、容易に自然酸化を受け、一
部の水酸化コバルトが導電性ネットワークの形成に寄与
できなくなることにより、電極利用率が低下してしま
う。In Comparative Example 2, the cobalt hydroxide having a small crystallite diameter was easily spontaneously oxidized, and some of the cobalt hydroxide could not contribute to the formation of the conductive network. Utilization rate decreases.
【００６０】以上から明らかなように、本発明によれ
ば、電極利用率に優れた電極を作製することが可能であ
る。As is clear from the above, according to the present invention, it is possible to produce an electrode having excellent electrode utilization.
【００６１】また、本発明の評価方法によれば、ペース
ト式電極の製造に適した活物質を選ぶことが可能であ
り、本発明の評価方法は、アルカリ二次電池評価の簡易
な代替評価方法として使用できることがわかる。Further, according to the evaluation method of the present invention, it is possible to select an active material suitable for the production of a paste electrode, and the evaluation method of the present invention is a simple alternative evaluation method for alkaline secondary battery evaluation. It can be seen that it can be used as.
【００６２】[0062]
【発明の効果】本発明によるタップ密度が高く、水酸化
コバルト被覆層を有する水酸化ニッケル粉末を用いるこ
とで、電極利用率に優れた電極を作製することが可能で
ある。By using the nickel hydroxide powder having a high tap density and a cobalt hydroxide coating layer according to the present invention, it is possible to produce an electrode having excellent electrode utilization.
【００６３】また、本発明の評価方法により、水酸化コ
バルト被覆層を有する水酸化ニッケル粉未の評価が可能
であり、ペースト式電極の製造に適した活物質を選ぶこ
とが可能である。Further, according to the evaluation method of the present invention, it is possible to evaluate a nickel hydroxide powder having a cobalt hydroxide coating layer, and it is possible to select an active material suitable for producing a paste electrode.
【図１】 水酸化コバルト被覆層を有する水酸化ニッケ
ル粉末の製造装置を示すシステム図である。FIG. 1 is a system diagram showing an apparatus for producing a nickel hydroxide powder having a cobalt hydroxide coating layer.
１ 水酸化ニッケル反応槽 ２ ニッケル塩水溶液供給ライン ３ アンモニウムイオン供給ライン ４ アルカリ金属水酸化物水溶液供給ライン ５ ｐＨセンサ ６ ｐＨコントローラ ７ 定量ポンプ ８ 温度センサ ９ 邪魔板 １０ 攪拌機 １１ 水酸化ニッケルオーバーフローライン １２ 水酸化コバルト被覆層反応槽 １３ コバルト塩水溶液供給ライン １４ アンモニウムイオン供給ライン １５ 不活性ガス供給ライン １６ 水酸化コバルトコートオーバーフローライン DESCRIPTION OF SYMBOLS 1 Nickel hydroxide reaction tank 2 Nickel salt aqueous solution supply line 3 Ammonium ion supply line 4 Alkali metal hydroxide aqueous solution supply line 5 pH sensor 6 pH controller 7 Metering pump 8 Temperature sensor 9 Baffle plate 10 Stirrer 11 Nickel hydroxide overflow line 12 Cobalt hydroxide coating layer reaction tank 13 Cobalt salt aqueous solution supply line 14 Ammonium ion supply line 15 Inert gas supply line 16 Cobalt hydroxide coat overflow line
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｇ０１Ｎ 1/36 Ｇ０１Ｎ 1/28 Ｚ (72)発明者 冨岡 大造 愛媛県新居浜市西原町３−５−３ 住友金 属鉱山株式会社別子事業所内 Ｆターム(参考） 2G001 AA01 BA18 CA01 FA09 FA18 GA14 KA08 KA10 MA04 RA10 4G048 AA02 AB01 AB02 AB04 AC06 AD03 AD06 AE05 5H050 AA08 BA11 CA03 CB14 DA09 EA12 FA17 FA18 GA02 GA10 GA12 GA13 GA28 HA05 HA10 HA13 HA14 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // G01N 1/36 G01N 1/28 Z (72) Inventor Daizo Tomioka 3-5 Nishiharacho, Niihama-shi, Ehime -3 Sumitomo Metal Mining Co., Ltd. Besshi Plant F term (reference) 2G001 AA01 BA18 CA01 FA09 FA18 GA14 KA08 KA10 MA04 RA10 4G048 AA02 AB01 AB02 AB04 AC06 AD03 AD06 AE05 5H050 AA08 BA11 CA03 CB14 DA09 EA12 FA17 FA18 GA10 GA12 GA28 HA05 HA10 HA13 HA14
Claims (7)
２９°以上０．８５１°以下である水酸化コバルトによ
り、表面が被覆されていることを特徴とするアルカリ二
次電池用水酸化ニッケル粉末。1. The half width obtained from the (101) plane is 0.2
Nickel hydroxide powder for an alkaline secondary battery, the surface of which is coated with cobalt hydroxide having a temperature of 29 ° or more and 0.851 ° or less.
０Å以上４５０Å以下である水酸化コバルトにより、表
面が被覆されていることを特徴とするアルカリ二次電池
用水酸化ニッケル粉末。2. The crystallite diameter determined from the (101) plane is 10
Nickel hydroxide powder for an alkaline secondary battery, the surface of which is coated with cobalt hydroxide of 0 ° or more and 450 ° or less.
れていることを特徴とする請求項１または２に記載のア
ルカリ二次電池用水酸化ニッケル粉末。3. The nickel hydroxide powder for an alkaline secondary battery according to claim 1, wherein the coating layer is formed of β-type cobalt hydroxide.
液とアンモニウムイオン供給体とを連続的に供給してろ
液とし、該ろ液中のニッケルイオン濃度が５〜８ｍｇ／
リットルになるように、ｐＨコントローラと連動させて
ｐＨを１１〜１３に維持し、槽内温度５０±１℃に保持
しつつ、アルカリ金属水酸化物水溶液を添加することに
より、球状水酸化ニッケルを製造する第１工程、第１工
程で生成した球状水酸化ニッケルを、スラリーごとオー
バーフローさせ、水酸化コバルト被覆層反応槽に連続し
て受け入れてろ液とし、コバルト水溶液とアンモニウム
イオン供給体と不活性ガスを該水酸化コバルト被覆層反
応槽に連続して供給し、該ろ液中のコバルトイオン濃度
が３〜６ｍｇ／リットルになるように、ｐＨコントロー
ラと連動させてｐＨを１１〜１３に維持し、槽内温度を
５０±１℃に保持しつつ、アルカリ金属水酸化物水溶液
を添加することにより、前記球状水酸化ニッケルの表面
に、水酸化コバルト被覆層を生成させる第２工程からな
るアルカリ二次電池用水酸化ニッケル粉末の製造方法。4. A nickel hydroxide reaction tank is continuously supplied with a nickel aqueous solution and an ammonium ion supplier to form a filtrate, and the nickel ion concentration in the filtrate is 5 to 8 mg / day.
The spherical nickel hydroxide is added by adding an alkali metal hydroxide aqueous solution while maintaining the tank temperature at 50 ± 1 ° C. while maintaining the pH at 11 to 13 in conjunction with a pH controller so as to obtain a liter. The first step of the production, the spherical nickel hydroxide produced in the first step is overflowed together with the slurry, and is continuously received in a cobalt hydroxide coating layer reaction tank to form a filtrate, a cobalt aqueous solution, an ammonium ion supplier and an inert gas. Is continuously supplied to the cobalt hydroxide coating layer reaction tank, and the pH is maintained at 11 to 13 in conjunction with a pH controller so that the cobalt ion concentration in the filtrate is 3 to 6 mg / liter. By adding an aqueous solution of an alkali metal hydroxide while maintaining the temperature in the tank at 50 ± 1 ° C., the surface of the spherical nickel hydroxide is coated with cobalt hydroxide. A method for producing a nickel hydroxide powder for an alkaline secondary battery, comprising a second step of forming a coating layer.
有する水酸化ニッケル粉末を浸漬し、攪拌混合し縣濁さ
せた後、水酸化コバルトを主とする縣濁部と、水酸化ニ
ッケルを主とする沈澱部とを、デカンテーション操作に
より分離し、前記縣濁部より水酸化コバルトを濾別回収
した後、前記回収物の粉体特性を評価することを特徴と
するアルカリ二次電池用水酸化ニッケル粉末の評価方
法。5. A nickel hydroxide powder having a cobalt hydroxide coating layer is immersed in an organic solvent, stirred, mixed and suspended. The main sedimentation part is separated by a decantation operation, and after collecting cobalt hydroxide from the suspension part by filtration, the powder characteristics of the recovered matter are evaluated. Evaluation method of nickel oxide powder.
下のアルコールであることを特徴とする請求項５に記載
のアルカリ二次電池用水酸化ニッケル粉末の評価方法。6. The method for evaluating nickel hydroxide powder for an alkaline secondary battery according to claim 5, wherein the organic solvent is an alcohol having a solubility parameter of 12 or less.
１）面の半価幅または（１０１）面の結晶子径を測定す
る請求項５に記載のアルカリ二次電池用水酸化ニッケル
粉末の評価方法。7. X-ray diffraction measurement of the recovered material,
The method for evaluating a nickel hydroxide powder for an alkaline secondary battery according to claim 5, wherein the half width of the 1) plane or the crystallite diameter of the (101) plane is measured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000108435A JP2001291515A (en) | 2000-04-10 | 2000-04-10 | Nickel hydroxide powder for alkaline secondary battery and its manufacturing method and evaluation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000108435A JP2001291515A (en) | 2000-04-10 | 2000-04-10 | Nickel hydroxide powder for alkaline secondary battery and its manufacturing method and evaluation method |
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| Publication Number | Publication Date |
|---|---|
| JP2001291515A true JP2001291515A (en) | 2001-10-19 |
Family
ID=18621274
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000108435A Pending JP2001291515A (en) | 2000-04-10 | 2000-04-10 | Nickel hydroxide powder for alkaline secondary battery and its manufacturing method and evaluation method |
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| Country | Link |
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| JP (1) | JP2001291515A (en) |
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| JP2008251392A (en) * | 2007-03-30 | 2008-10-16 | Tanaka Chemical Corp | Active material for nickel positive electrode, and manufacturing method thereof |
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| JP2008251392A (en) * | 2007-03-30 | 2008-10-16 | Tanaka Chemical Corp | Active material for nickel positive electrode, and manufacturing method thereof |
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| JP2010159180A (en) * | 2009-01-08 | 2010-07-22 | Tanaka Chemical Corp | Method for producing agglomerated crystal particle useful as nickel positive electrode active material |
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