JP4846309B2 - Method for producing nickel manganese cobalt composite oxide - Google Patents
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- JP4846309B2 JP4846309B2 JP2005262378A JP2005262378A JP4846309B2 JP 4846309 B2 JP4846309 B2 JP 4846309B2 JP 2005262378 A JP2005262378 A JP 2005262378A JP 2005262378 A JP2005262378 A JP 2005262378A JP 4846309 B2 JP4846309 B2 JP 4846309B2
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Description
本発明はニッケルマンガンコバルト複合酸化物及びその製造方法に関する。 The present invention relates to a nickel manganese cobalt composite oxide and a method for producing the same.
近年、リチウムイオン二次電池用の正極活物質としてのリチウムニッケル酸化物に他の成分を含ませて充放電サイクル特性、高温安定性を向上させる目的で、リチウムニッケル酸化物を製造する原料としての水酸化ニッケルに他の成分を含ませる試みがなされている（特許文献１）。特に高温下で、安定した高い利用率を持ち、サイクル劣化の少ない高コバルトおよびマンガンを含む水酸化ニッケルの開発が重要な課題となっている。係る課題を解決すべく最近本発明者等による、高密度のコバルトマンガン共沈水酸化ニッケル及びその製造方法の開発を促した（特許文献２）。
本発明は、充放電サイクル特性、高温安定性に優れたリチウムイオン二次電池用の正極活物質原料たるニッケルマンガンコバルト複合酸化物及びその製造法に関するものである。 The present invention relates to a nickel manganese cobalt composite oxide as a positive electrode active material material for a lithium ion secondary battery excellent in charge / discharge cycle characteristics and high-temperature stability, and a method for producing the same.
本発明者は上記課題を解決すべくさらに鋭意研究した結果、水溶液中で酸化条件下で、十分な攪拌を行いながら、コバルト塩およびマンガン塩を含むニッケル塩水溶液、錯化剤、並びにアルカリ金属水酸化物を連続供給して連続結晶成長させ、連続に取り出すことにより、ニッケルマンガンコバルト複合酸化物の粒子を得ることができることを見出し本発明を完成した。 As a result of further diligent research to solve the above-mentioned problems, the present inventor has found that an aqueous nickel salt solution containing a cobalt salt and a manganese salt, a complexing agent, and an alkali metal water while sufficiently stirring under oxidizing conditions in an aqueous solution. The present invention was completed by finding that nickel manganese cobalt composite oxide particles can be obtained by continuously supplying oxides, continuously growing crystals, and continuously taking them out.
すなわち、本発明は、次式で表される、ニッケルマンガンコバルト複合酸化物粒子に関する。 That is, the present invention relates to nickel manganese cobalt composite oxide particles represented by the following formula.
（Ｎｉ（１−ｘ−ｙ）ＣｏｘＭｎｙ）ＯＯＨ
（ここでＸ、Ｙは次の関係を満たす。１／２０≦ｘ≦１／３、１／２０≦ｙ≦１／３）
(Ni (1-x-y ) Co x Mn y) OOH
(Where X and Y satisfy the following relationship: 1/20 ≦ x ≦ 1/3, 1/20 ≦ y ≦ 1/3)
また本発明は、平均粒径が、５〜１５μｍである前記のニッケルマンガンコバルト複合酸化物粒子に関する。 Moreover, this invention relates to the said nickel manganese cobalt complex oxide particle whose average particle diameter is 5-15 micrometers.
さらに本発明はニッケルマンガンコバルト複合酸化物粒子の製造方法である。すなわち、反応槽内に、酸化条件下で、コバルト（２＋）塩およびマンガン（２＋）塩を含むニッケル（２＋）塩水溶液と、アルカリ金属水酸化物とを連続供給して連続的に反応させて結晶を成長させ、連続的に取り出すことを特徴とする。 Furthermore, the present invention is a method for producing nickel manganese cobalt composite oxide particles. That is, a nickel (2+) salt aqueous solution containing a cobalt (2+) salt and a manganese (2+) salt and an alkali metal hydroxide are continuously fed into the reaction vessel under oxidizing conditions to continuously react. Crystals are grown and continuously taken out.
また本発明は、前記酸化条件が、酸化剤の存在の下で反応させることを特徴とするニッケルマンガンコバルト複合酸化物粒子の製造方法である。ここで前記酸化剤には、塩素、臭素、次亜塩素酸塩、塩素酸塩、オゾンまたは過酸化水素等の化学的酸化剤のみならず電解酸化により発生する電解酸化種を含む。 Moreover, this invention is a manufacturing method of the nickel manganese cobalt complex oxide particle characterized by making the said oxidation conditions react in presence of an oxidizing agent. Here, the oxidizing agent includes not only chemical oxidizing agents such as chlorine, bromine, hypochlorite, chlorate, ozone or hydrogen peroxide but also electrolytically oxidized species generated by electrolytic oxidation.
また、本発明は、前記酸化条件が、酸化触媒の存在の下で、空気と接触させて反応させることを特徴とするニッケルマンガンコバルト複合酸化物粒子の製造方法である。ここで本発明には、酸化剤が、鉄、ニッケル、クロムのいずれか一種の金属又はそれらのイオンであることを特徴とする発明を含む。 Further, the present invention is the method for producing nickel manganese cobalt composite oxide particles, characterized in that the oxidation conditions are caused to react with air in the presence of an oxidation catalyst. Here, the present invention includes an invention characterized in that the oxidizing agent is any one of iron, nickel and chromium, or ions thereof.
また、本発明においては、錯化剤を添加する方法をも含む。 The present invention also includes a method of adding a complexing agent.
本発明の製造方法により、ほぼ球状の、ニッケルマンガンコバルト複合酸化物粒子を製造することができる。 By the production method of the present invention, approximately spherical nickel manganese cobalt composite oxide particles can be produced.
（ニッケルマンガンコバルト複合酸化物粒子）
本発明にかかるニッケルマンガンコバルト複合酸化物粒子は黒色である。本発明にかかるニッケルマンガンコバルト複合酸化物の粒子物性（バルク密度、タッピング密度、比表面積、平均粒径、粒径分布等）は従来公知の種々の測定装置により行うことが可能である。具体的にはタッピング密度は１ｇ／ｃｍ ３ 以上であり、比表面積は８〜２０ｍ２／ｇの範囲であり、また図１に示されるように平均粒径は５〜１５μｍの範囲でありほぼ球状である。
(Nickel manganese cobalt composite oxide particles)
The nickel manganese cobalt composite oxide particles according to the present invention are black. The particle physical properties (bulk density, tapping density, specific surface area, average particle size, particle size distribution, etc.) of the nickel manganese cobalt composite oxide according to the present invention can be measured by various conventionally known measuring devices. Specifically, the tapping density is 1 g / cm 3 or more, the specific surface area is in the range of 8 to 20 m 2 / g, and the average particle diameter is in the range of 5 to 15 μm as shown in FIG. It is.
本発明にかかるニッケルマンガンコバルト複合酸化物粒子は形式的に、（Ｎｉ（１−ｘ−ｙ）ＣｏｘＭｎｙ）ＯＯＨと表すことができる。ここでニッケル、コバルト、マンガンの含有量には特に制限はないが、１／２０≦ｘ≦１／３、１／２０≦ｙ≦１／３であることが好ましい。ニッケル、コバルト、マンガンの含有量は、通常公知の金属分析方法により可能である。例えば、Ｘ線分析、原子吸光分析等の物理的分析方法、及び化学的分析方法が挙げられる。 The nickel manganese cobalt composite oxide particles according to the present invention can be formally expressed as (Ni (1-xy) Co x Mn y ) OOH. Here, the contents of nickel, cobalt, and manganese are not particularly limited, but preferably 1/20 ≦ x ≦ 1/3 and 1/20 ≦ y ≦ 1/3. The contents of nickel, cobalt, and manganese can be usually obtained by a known metal analysis method. Examples thereof include physical analysis methods such as X-ray analysis and atomic absorption analysis, and chemical analysis methods.
本発明にかかるニッケルマンガンコバルト複合酸化物の酸化状態は、すでに知られているニッケルコバルトマンガン水酸化物、（Ｎｉ（１−ｘ−ｙ）ＣｏｘＭｎｙ）（ＯＨ）２（特開２００２−２０１０２８）と比較して１酸化数高いことを特徴とする。本発明においてはかかる酸化状態が、主にニッケル、コバルト、マンガンに不均一に分布している場合も、これら金属に均一に分布している場合も含む。本発明の複合酸化物の正確な酸化状態は、通常の種々の物理的、又は化学的測定方法により決めることができる。本発明においては特に、ヨウ素による酸化還元滴定方法の使用が好ましい。 The oxidation state of the nickel manganese cobalt composite oxide according to the present invention is the known nickel cobalt manganese hydroxide, (Ni (1-xy) Co x Mn y ) (OH) 2 Compared with 201028), it is characterized by a higher oxidation number. In the present invention, the oxidation state mainly includes non-uniform distribution in nickel, cobalt, and manganese, and includes a case in which the oxidation state is uniformly distributed in these metals. The exact oxidation state of the composite oxide of the present invention can be determined by various usual physical or chemical measurement methods. In the present invention, it is particularly preferable to use a redox titration method with iodine.
（製造方法）
本発明にかかるニッケルマンガンコバルト複合酸化物粒子の製造方法は、連続反応用の反応槽に、十分な攪拌をしつつ、酸化条件下で、コバルト塩（コバルト（ＩＩ）イオン）およびマンガン塩（マンガン（ＩＩ）イオン）、ニッケル塩（ニッケル（ＩＩ）イオン）の混合水溶液に、特定のｐＨ値を維持しつつアルカリ金属水酸化物を連続的に供給して反応させて結晶を生成させ、該成長した結晶の沈殿物粒子を連続的に反応槽から取り出すことにより、連続的にニッケルマンガンコバルト複合酸化物粒子を製造することを特徴とする。
(Production method)
The method for producing nickel manganese cobalt composite oxide particles according to the present invention comprises a cobalt salt (cobalt (II) ion) and a manganese salt (manganese) under oxidizing conditions while stirring sufficiently in a reaction tank for continuous reaction. (II) ions), nickel salt (nickel (II) ions) mixed aqueous solution, while maintaining a specific pH value, alkali metal hydroxide is continuously supplied to react to form crystals, and the growth The nickel manganese cobalt composite oxide particles are continuously produced by continuously taking out the precipitated particles of the crystals from the reaction vessel.
係る連続反応のための反応槽については特に制限はないが、生成する粒子を適時連続的に取り出すことのできる装置が設けてあれば好ましい。具体的には公知のオーバーフローパイプが挙げられる。 Although there is no restriction | limiting in particular about the reaction tank for such a continuous reaction, It is preferable if the apparatus which can take out the particle | grains to produce | generate continuously timely is provided. Specifically, a well-known overflow pipe is mentioned.
反応は、反応槽内の酸化条件、塩濃度、ｐＨ、温度、攪拌条件を一定範囲内に維持することにより、金属イオンの存在比、結晶度、タッピング密度、比表面積、粒子径等の化学的物性、及び粉体物性が好ましく制御される。特に金属イオンの存在比は、仕込みのニッケルイオン、コバルトイオン、マンガンイオンの量を望ましいモル比に適宜設定することにより、容易にそのモル比を有するにニッケルマンガンコバルト複合酸化物粒子を得ることができる。 The reaction is carried out by maintaining the oxidation conditions, salt concentration, pH, temperature, and stirring conditions in the reaction tank within a certain range, so that chemical ratios such as the abundance ratio of metal ions, crystallinity, tapping density, specific surface area, particle size, etc. The physical properties and powder physical properties are preferably controlled. In particular, the abundance ratio of the metal ions can be easily obtained by setting the amounts of the charged nickel ions, cobalt ions, and manganese ions to a desired molar ratio, thereby easily obtaining nickel manganese cobalt composite oxide particles having the molar ratio. it can.
本発明により得られるニッケルマンガンコバルト複合酸化物粒子は、（Ｎｉ（１-ｘ-ｙ）ＣｏｘＭｎｙ）（ＯＯＨ）と表した場合において、１／２０≦ｘ≦１／３、１／２０≦ｙ≦１／３であり、タッピング密度が１ｇ／ｃｍ ３ 以上、比表面積が８〜３０ｍ２／ｇ、平均粒径が５〜１５μｍであることを特徴とする。 The nickel manganese cobalt composite oxide particles obtained by the present invention are expressed as (Ni (1-xy) Co x Mn y ) (OOH), 1/20 ≦ x ≦ 1/3, 1/20. ≦ y ≦ 1/3, tapping density is 1 g / cm 3 or more, specific surface area is 8 to 30 m 2 / g, and average particle size is 5 to 15 μm.
本発明による製造方法はアルカリ水溶液を混合することを特徴とするが、アルカリ水溶液としては特に制限はないが、アルカリ金属水酸化物の水溶液、アンモニア水溶液の使用が好ましい。本発明においては以下説明するように錯化作用をも有するアンモニア水溶液の使用が好ましい。 The production method according to the present invention is characterized in that an alkaline aqueous solution is mixed. The alkaline aqueous solution is not particularly limited, but an aqueous alkali metal hydroxide solution or an aqueous ammonia solution is preferably used. In the present invention, it is preferable to use an aqueous ammonia solution having a complexing action as described below.
反応槽内の各金属イオンの塩濃度は、それぞれ５０〜２００ｍＳ／ｃｍの範囲で±５ｍＳ／ｃｍ内に保持し、アンモニウムイオン濃度を１〜１０ｇ／Ｌの範囲で±０．５ｇ／Ｌ内に保持することが好ましい。 The salt concentration of each metal ion in the reaction vessel is kept within ± 5 mS / cm in the range of 50 to 200 mS / cm, and the ammonium ion concentration is within ± 0.5 g / L in the range of 1 to 10 g / L. It is preferable to hold.
又、反応ｐＨを１１．０〜１３．０の範囲で±０．０５内に保持することが好ましく、反応中にｐＨ値をモニターし、必要ならばアルカリ金属水酸化物溶液の添加によりｐＨを調節することができる。 The reaction pH is preferably maintained within ± 0.05 in the range of 11.0 to 13.0. The pH value is monitored during the reaction, and if necessary, the pH is adjusted by adding an alkali metal hydroxide solution. Can be adjusted.
反応温度は２５〜８０℃の範囲で±０．５℃内に保持することが好ましい。温度調節は従来公知の外部ヒーター、内部ヒーター加熱方式のどちらでも使用可能である。 The reaction temperature is preferably maintained within ± 0.5 ° C in the range of 25-80 ° C. The temperature adjustment can be performed using either a conventionally known external heater or internal heater heating method.
塩濃度の調節剤としては、塩化ナトリウム、塩化カリウム、硫酸ナトリウム、硫酸カリウム、塩酸アンモニウム、硫酸アンモニウム等が挙げられる。カルシウム塩としては、硝酸塩や酢酸塩やシュウ酸塩等が用いられる。 Examples of the salt concentration regulator include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium hydrochloride, and ammonium sulfate. As the calcium salt, nitrate, acetate, oxalate, or the like is used.
本発明にかかる製造方法は、反応を酸化条件下で行うことを特徴とする。酸化条件については特に制限はないが、特に本発明では、酸化剤を用いる方法と酸化触媒存在下空気接触によるどちらかの方法を使用することが好ましい。 The production method according to the present invention is characterized in that the reaction is carried out under oxidizing conditions. The oxidation conditions are not particularly limited, but in the present invention, it is particularly preferable to use either a method using an oxidizing agent or a method using air contact in the presence of an oxidation catalyst.
酸化剤としては、水溶液で使用可能な種々の無機、有機酸化剤が使用可能である。本発明においては特に、無機酸化剤の使用が好ましい。具体的には塩素、臭素、塩素酸塩、次亜塩素酸塩、過酸化水素が挙げられる。酸化剤は反応溶液に予め添加してもよいし、アルカリ水溶液に混合して添加してもよい。また酸化剤水溶液を別に反応槽に添加してもよい。酸化触媒の使用量は、全金属イオン濃度を１当量とした場合ついて、１．２酸化当量〜２．５酸化当量であることが好ましい。 As the oxidizing agent, various inorganic and organic oxidizing agents that can be used in an aqueous solution can be used. In the present invention, it is particularly preferable to use an inorganic oxidizing agent. Specific examples include chlorine, bromine, chlorate, hypochlorite, and hydrogen peroxide. The oxidizing agent may be added in advance to the reaction solution, or may be added to the alkaline aqueous solution. Moreover, you may add an oxidizing agent aqueous solution to a reaction tank separately. The amount of the oxidation catalyst used is preferably 1.2 oxidation equivalent to 2.5 oxidation equivalent when the total metal ion concentration is 1 equivalent.
また、本発明の製造方法においては好ましくは適当な酸化触媒の存在下空気接触による方法である。空気接触とは、反応溶液中に空気雰囲気中空気を吹き込むことで実施することができる。ここで吹き込む空気には、空気自体の他、不活性気体に混合して希釈した空気や、酸素を混合した空気も含む意味である。酸化触媒としては、原料として含まれる種々のいわゆる高酸化数のコバルト、ニッケル、マンガンイオンの他、添加された鉄、ニッケル、クロムイオンのいずれかが含まれる。反応槽がステンレス製である場合、これらの金属又はイオンが微量含まれることになり酸化触媒としての作用を奏する。 Further, in the production method of the present invention, a method by contact with air in the presence of an appropriate oxidation catalyst is preferred. The air contact can be performed by blowing air in an air atmosphere into the reaction solution. The air blown in here means not only air itself but also air diluted with an inert gas and air mixed with oxygen. The oxidation catalyst includes various so-called high oxidation number cobalt, nickel and manganese ions contained as raw materials, and any of added iron, nickel and chromium ions. When the reaction vessel is made of stainless steel, a trace amount of these metals or ions are contained, and the effect as an oxidation catalyst is exhibited.
また、一般に水溶液中より固体結晶を析出する際、その濃度勾配が大きいと微粒子の析出が多くなる。つまり、水溶液中より固体結晶を析出させるメカニズムは、水溶液が準飽和状態→飽和状態→過飽和状態→結晶析出となる。粒子を成長させるには上記メカニズムをできるだけゆっくりスムーズに行う必要があり、そのためには、飽和状態付近の濃度勾配を小さく取る必要がある。ところが、ニッケルやコバルト、マンガンの水酸化物の溶解度曲線はｐＨに対し、非常に大きく変化する。つまり、水溶液中で、ｐＨに対する金属イオンの濃度勾配が非常に大きい。従って、通常の方法では微粒子の生成しか望めない。本発明においては、金属イオンをアンモニウム錯塩とすることにより、水溶液中でのｐＨに対する金属イオンの濃度勾配を小さくし粒子の成長を行うことが好ましい。 In general, when solid crystals are precipitated from an aqueous solution, if the concentration gradient is large, the precipitation of fine particles increases. That is, the mechanism for precipitating solid crystals from an aqueous solution is that the aqueous solution is in a semi-saturated state → saturated state → supersaturated state → crystal precipitation. In order to grow the particles, it is necessary to perform the above mechanism as smoothly and smoothly as possible. For this purpose, it is necessary to make the concentration gradient near the saturation state small. However, the solubility curves of nickel, cobalt, and manganese hydroxides vary greatly with pH. That is, the concentration gradient of metal ions with respect to pH is very large in an aqueous solution. Therefore, only the production of fine particles can be expected by the usual method. In the present invention, it is preferable to grow particles by reducing the concentration gradient of metal ions with respect to pH in an aqueous solution by using metal ions as ammonium complex salts.
さらにｐＨをコントロ−ルするだけでは、アンモニアの分解や蒸発により液中のアンモニウムイオン濃度が変化し、アンモニウム錯塩から生じる結晶核の発生が不安定になる。液中のアンモニウムイオン濃度をコントロ−ルすることによって初めて結晶核の発生が一定となり、粒子の成長度が揃ったものとなる。上記メカニズムの状態を保持するには、必要とする金属イオン量に見合うアンモニウムイオン供給体、アルカリ金属水酸化物を常に必要とするため、反応工程は連続とすることが好ましい。ここで、撹拌速度を早くすることにより、粒子同士の研磨作用が合わさり、研磨・成長を繰り返しながら、流動性の伴う球状の高密度粒子が得られることとなる。 Furthermore, if only the pH is controlled, the ammonium ion concentration in the liquid changes due to the decomposition and evaporation of ammonia, and the generation of crystal nuclei resulting from the ammonium complex salt becomes unstable. Only by controlling the ammonium ion concentration in the liquid, the generation of crystal nuclei becomes constant and the degree of growth of the particles becomes uniform. In order to maintain the state of the above mechanism, an ammonium ion supplier and an alkali metal hydroxide corresponding to the amount of metal ions required are always required, and therefore the reaction process is preferably continuous. Here, by increasing the stirring speed, the polishing action of the particles is combined, and spherical high density particles with fluidity are obtained while repeating polishing and growth.
本発明における反応は的様な錯化剤の併用も好ましい。錯化剤は特に限定されるものではないが、アンモニウムイオンが好ましい。アンモニウムイオン供給体は、反応式（１）、（２）で表されるごとく、反応中間体として使用されるものである。ニッケル塩、アンモニウムイオン供給体、アルカリ金属水酸化物をそれぞれ硫酸ニッケル、アンモニア、水酸化ナトリウムの場合を示す（式を単純にするため、コバルト、マンガンは省いたが同じようにアンモニウム錯塩を経由する）。化式から明らかなように、４当量以上のアンモニアは必要なく、せいぜい０．５当量程度あればよい。 The reaction in the present invention is preferably performed in combination with a suitable complexing agent. The complexing agent is not particularly limited, but ammonium ions are preferable. The ammonium ion supplier is used as a reaction intermediate as represented by the reaction formulas (1) and (2). Nickel salt, ammonium ion supplier, and alkali metal hydroxide are nickel sulfate, ammonia, and sodium hydroxide, respectively (Cobalt and manganese are omitted to simplify the formula, but the same goes through ammonium complex salt. ). As is apparent from the chemical formula, ammonia of 4 equivalents or more is not necessary, and it may be about 0.5 equivalents at most.
ＮｉＳＯ４＋４ＮＨ３＋２ＮａＯＨ → Ｎｉ（ＮＨ３）４（ＯＨ）２＋Ｎａ２ＳＯ４ （１）
Ｎｉ（ＮＨ３）４（ＯＨ）２ → Ｎｉ（ＯＨ）２＋４ＮＨ３ （２）
NiSO 4 + 4NH 3 + 2NaOH → Ni (NH 3 ) 4 (OH) 2 + Na 2 SO 4 (1)
Ni (NH 3 ) 4 (OH) 2 → Ni (OH) 2 + 4NH 3 (2)
以上説明した本発明の反応原料、反応条件を満たすべく反応は次の手順で実施することが好ましい。 In order to satisfy the reaction raw materials and reaction conditions of the present invention described above, the reaction is preferably carried out by the following procedure.
通常のプロペラタイプの攪拌羽根を備えた攪拌機と、オーバーフローパイプを備えたステンレス製円筒形反応槽を用いることが好ましい。まず反応槽に水を入れ、ｐＨが所定の値になるまで水酸化ナトリウム溶液を加え、電熱ヒータで反応溶液の温度を所定の範囲に保持する。 It is preferable to use a stirrer equipped with a normal propeller type stirring blade and a stainless steel cylindrical reaction tank equipped with an overflow pipe. First, water is put into the reaction vessel, a sodium hydroxide solution is added until the pH reaches a predetermined value, and the temperature of the reaction solution is maintained within a predetermined range with an electric heater.
次いで反応槽内の溶液中に十分空気が含まれるように一定速度で攪拌する。さらに反応槽に空気を連続的に吹き込み反応槽内の雰囲気を酸素雰囲気とする。 Next, the solution in the reaction vessel is stirred at a constant speed so that air is sufficiently contained. Further, air is continuously blown into the reaction tank to make the atmosphere in the reaction tank an oxygen atmosphere.
次に反応槽内に所定のモル比の濃度となるようにニッケル（２＋）イオン、コバルト（２＋）イオン、マンガン（２＋）イオン原料塩を混合する。 Next, nickel (2+) ions, cobalt (2+) ions, and manganese (2+) ion raw material salts are mixed in the reaction tank so as to have a concentration of a predetermined molar ratio.
その混合溶液中に所定の濃度のアンモニア水溶液を一定速度にて連続供給する。同時に反応槽内の溶液のｐＨを所定に範囲に維持するため酸化ナトリウムを断続的に加える。 An aqueous ammonia solution having a predetermined concentration is continuously supplied into the mixed solution at a constant rate. At the same time, sodium oxide is intermittently added to maintain the pH of the solution in the reaction vessel within a predetermined range.
所定の時間経過後反応が定常状態であることを確認し、オーバーフローパイプより生成物粒子を連続的に２４時間別の反応槽に移送して採取し、水洗後、濾過して分離する。分離された粒子は適当な条件で加熱乾燥する。 After a predetermined time has passed, it is confirmed that the reaction is in a steady state, and product particles are continuously transferred from an overflow pipe to another reaction vessel for 24 hours, collected, washed with water, and filtered to separate. The separated particles are heat-dried under appropriate conditions.
以下本発明を実施例に則してさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail according to an Example, this invention is not limited to these Examples.
（実施例１）
７０φプロペラタイプの攪拌羽根１ 枚を備えた攪拌機とオーバーフローパイプを備えた有効容積１５Ｌのステンレス（ＳＵＳ３０４）製円筒形反応槽に水を１３Ｌ入れた。次いでｐＨが１２．０になるまで３０％水酸化ナトリウム溶液を加え、電熱ヒータで温度を６０℃に保持した。次いで反応槽内の溶液中に十分空気が含まれるように一定速度で攪拌した。また、反応槽に空気を０．５Ｌ／分の流量で連続的に吹き込み反応槽内の雰囲気を酸素雰囲気とした。次に１．７ｍｏｌ／Ｌの硫酸ニッケル液と１．５ｍｏｌ／Ｌ硫酸コバルト液と１．１ｍｏｌ／Ｌ硫酸マンガン水溶液をＮｉ：Ｃｏ：Ｍｎ＝１：１：１（モル比）となるように混合した。その混合溶液中にアンモニウムイオンを１Ｌあたり１００ｇ含む硫酸アンモニウム溶液を用いてアンモニア濃度が５ｇ／Ｌになるように混合し、その溶液を１０ｃｍ ３ ／分の一定速度にて連続供給した。さらに、反応槽内の溶液のｐＨが１２ ．０に維持するために３０％水酸化ナトリウムを断続的に加えた。
Example 1
13 L of water was put into a stainless steel (SUS304) cylindrical reaction tank having an effective volume of 15 L equipped with a stirrer equipped with one 70φ propeller type stirring blade and an overflow pipe. Next, a 30% sodium hydroxide solution was added until the pH reached 12.0, and the temperature was maintained at 60 ° C. with an electric heater. Subsequently, the solution in the reaction vessel was stirred at a constant speed so that air was sufficiently contained. In addition, air was continuously blown into the reaction tank at a flow rate of 0.5 L / min, and the atmosphere in the reaction tank was an oxygen atmosphere. Next, a 1.7 mol / L nickel sulfate solution, a 1.5 mol / L cobalt sulfate solution, and a 1.1 mol / L manganese sulfate aqueous solution were mixed so that Ni: Co: Mn = 1: 1: 1 (molar ratio). did. The mixed solution was mixed with an ammonium sulfate solution containing 100 g of ammonium ions per liter so that the ammonia concentration was 5 g / L, and the solution was continuously supplied at a constant rate of 10 cm 3 / min. Furthermore, the pH of the solution in the reaction vessel is 12. 30% sodium hydroxide was added intermittently to maintain zero.
反応が定常状態になった７２時間後にオーバーフローパイプより生成物粒子を連続的に２４時間採取し水洗後、濾過して分離し１００℃にて１５時間乾燥して黒色粉末としてニッケルマンガンコバルト複合酸化物粒子を得た。 72 hours after the reaction reaches a steady state, product particles are continuously collected from the overflow pipe for 24 hours, washed with water, separated by filtration, dried at 100 ° C. for 15 hours, and nickel manganese cobalt composite oxide as a black powder. Particles were obtained.
得られたニッケルマンガンコバルト複合酸化物粒子のタッピング密度を以下のように測定した。
試料の調整：２０ｍＬセルの質量を測定し［Ａ］、４８ｍｅｓｈのフルイで結晶をセルに自然落下して充填した。４ｃｍスペーサー装着の株式会社セイシン企業製、「ＴＡＰＤ ＥＮＳＥＲ ＫＹＴ３０００」を用いて２００回タッピング後セルの質量［Ｂ］と充填容積［Ｄ］を測定した。次式により計算した。
タップ密度＝（Ｂ−Ａ）／Ｄ ｇ／ｍｌかさ密度＝（Ｂ−Ａ）／Ｃ ｇ／ｍｌ測定結果：タップ密度＝１．０５ｇ／ｃｍ ３
The tapping density of the obtained nickel manganese cobalt composite oxide particles was measured as follows.
Preparation of sample: The mass of a 20 mL cell was measured [A], and the crystal was spontaneously dropped into the cell and filled with a 48 mesh sieve. The mass [B] and the filling volume [D] of the cell after tapping 200 times were measured using “TAPD ENSER KYT3000” manufactured by Seishin Co., Ltd. equipped with a 4 cm spacer. The following formula was used for calculation.
Tap density = (BA) / D g / ml Bulk density = (BA) / C g / ml Measurement result: Tap density = 1.05 g / cm 3
上で得られたニッケルマンガンコバルト複合酸化物粒子の平均粒径は、堀場製作所製ＬＡ−９１０を使用し操作手順書に従い測定し、９．２３μｍであった。 The average particle diameter of the nickel manganese cobalt composite oxide particles obtained above was 9.23 μm as measured according to the operating procedure using LA-910 manufactured by Horiba.
図１には得られたニッケルマンガンコバルト複合酸化物粒子の電子顕微鏡写真を示した。ほぼ球状の粒子であることが分かる。 FIG. 1 shows an electron micrograph of the obtained nickel manganese cobalt composite oxide particles. It turns out that it is a substantially spherical particle.
（実施例２）
硫酸ニッケル液、硫酸コバルト液、硫酸マンガン液を体積比３０：１８：２０の割合で混合し、ニッケルマンガンコバルト複合酸化物粒子を形成させる反応溶液のｐＨを１１．８とした他は実施例１と同様の条件でＮｉ：Ｃｏ：Ｍｎ＝５０：２０：３０であるニッケルマンガンコバルト複合酸化物を製造した。得られた粒子のタッピング密度は０．９３ｇ／ｃｍ ３ であった。
(Example 2)
Example 1 except that a nickel sulfate cobalt solution, a cobalt sulfate solution, and a manganese sulfate solution were mixed at a volume ratio of 30:18:20, and the pH of the reaction solution for forming nickel manganese cobalt composite oxide particles was set to 11.8. A nickel manganese cobalt composite oxide having Ni: Co: Mn = 50: 20: 30 was produced under the same conditions as those described above. The tapping density of the obtained particles was 0.93 g / cm 3 .
以上説明した実施例では、特定のＮｉ：Ｃｏ：Ｍｎモル比の例であるが、同様の反応装置、反応条件を使用し、種々のＮｉ：Ｃｏ：Ｍｎモル比を有する混合溶液を原料として用いることにより、本発明に含まれる全てのモル比のニッケルマンガンコバルト複合酸化物粒子を得ることが可能である。 The above-described embodiments are examples of specific Ni: Co: Mn molar ratios, but the same reaction apparatus and reaction conditions are used, and mixed solutions having various Ni: Co: Mn molar ratios are used as raw materials. By this, it is possible to obtain nickel manganese cobalt composite oxide particles of all molar ratios included in the present invention.
本発明により、次式で表されるニッケルマンガンコバルト複合酸化物粒子を得る。かかる新規な複合酸化物は、リチウムイオン二次電池用の正極活物質として使用して、充放電サイクル特性、高温安定性を向上させることが可能となる
（Ｎｉ（１−ｘ−ｙ）ＣｏｘＭｎｙ）ＯＯＨ
（ここでＸ、Ｙは次の関係を満たす。１／２０≦ｘ≦１／３、１／２０≦ｙ≦１／３）
According to the present invention, nickel manganese cobalt composite oxide particles represented by the following formula are obtained. Such a novel composite oxide can be used as a positive electrode active material for a lithium ion secondary battery to improve charge / discharge cycle characteristics and high-temperature stability. (Ni (1-xy) Co x Mn y) OOH
(Where X and Y satisfy the following relationship: 1/20 ≦ x ≦ 1/3, 1/20 ≦ y ≦ 1/3)
Claims (3)
（Ｎｉ（１−ｘ−ｙ）ＣｏｘＭｎｙ）ＯＯＨ
（ここでｘ、ｙは次の関係を満たす。１／２０≦ｘ≦１／３、１／２０≦ｙ≦１／３）
で表されるニッケルマンガンコバルト複合酸化物粒子の製造方法であって、反応槽内に、空気雰囲気中または酸化剤存在下、コバルト（２＋）塩およびマンガン（２＋）塩を含むニッケル（２＋）塩水溶液、錯化剤、並びにアルカリ金属水酸化物を連続供給し、連続結晶成長させ、連続的に取り出すことを特徴とする製造方法。 The following formula:
(Ni (1-xy) CoxMny) OOH
(Where x and y satisfy the following relationship: 1/20 ≦ x ≦ 1/3, 1/20 ≦ y ≦ 1/3)
A nickel (2+) salt containing a cobalt (2+) salt and a manganese (2+) salt in a reaction vessel in an air atmosphere or in the presence of an oxidizing agent. aqueous solution, complexing agent, and an alkali metal hydroxide was continuously fed, was continuously grown, manufacturing method manufactured you characterized by continuously withdrawing.
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