JP2003221236A5 - - Google Patents
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【特許請求の範囲】
【請求項１】 一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表され、一次粒子が凝集して二次粒子を形成した複合酸化物であり、その一次粒子の平均粒子径が０．３〜３μｍであり、二次粒子の平均粒子径が５〜２０μｍであって、ＢＥＴ比表面積が０．３〜２ｍ 2 ／ｇであることを特徴とするリチウム含有複合酸化物。
【請求項２】 前記一般式において、ｙ＞０であり、Ｍが少なくともＣｏを含む１種以上の元素であることを特徴とする請求項１に記載のリチウム含有複合酸化物。
【請求項３】 前記一般式において、ｙ＝１／６であることを特徴とする請求項１または２に記載のリチウム含有複合酸化物。
【請求項４】 前記一般式において、ｙ＝１／３であることを特徴とする請求項１または２に記載のリチウム含有複合酸化物。
【請求項５】 ＮｉとＭｎの量比が１：１であることを特徴とする請求項１〜４のいずれかに記載のリチウム含有複合酸化物。
【請求項６】 リチウム含有複合酸化物を活物質とする正極および負極と非水電解質を備えた非水二次電池であって、上記複合酸化物が、請求項１〜５のいずれかに記載のリチウム含有複合酸化物であることを特徴とする非水二次電池。
【請求項７】 リチウム含有複合酸化物を活物質とする正極および負極と非水電解質を備えた非水二次電池であって、上記複合酸化物として、少なくとも、一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表され、一次粒子が凝集して二次粒子を形成した複合酸化物であり、その二次粒子の平均粒子径が５〜２０μｍであるリチウム含有複合酸化物Ａと、前記複合酸化物Ａの二次粒子の平均粒子径よりも小さい平均粒子径を有するリチウム含有複合酸化物Ｂとを混合して用いたことを特徴とする非水二次電池。
【請求項８】 リチウム含有複合酸化物Ｂの割合が、正極活物質全体の１０〜４０重量％であることを特徴とする請求項７に記載の非水二次電池。
【請求項９】 リチウム含有複合酸化物Ｂの平均粒子径が、リチウム含有複合酸化物Ａの二次粒子の平均粒子径の３／５以下であることを特徴とする請求項７または８に記載の非水二次電池。
【請求項１０】 リチウム含有複合酸化物Ｂが、一次粒子が凝集して二次粒子を形成した複合酸化物であることを特徴とする請求項７〜９のいずれかに記載の非水二次電池。
【請求項１１】 リチウム含有複合酸化物Ｂが、リチウム含有複合酸化物Ａと同一組成であるか、または一般式Ｌｉ1+a+bＲ1-aＯ2［ただし、０≦ａ≦０．０５、−０．０５≦ａ＋ｂ≦０．０５であって、ＲはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択され、少なくともＣｏを含む１種以上の元素］で表されることを特徴とする請求項７〜１０のいずれかに記載の非水二次電池。
【請求項１２】 前記リチウム含有複合酸化物Ａを表す一般式において、ｙ＞０であり、Ｍが少なくともＣｏを含む１種以上の元素であることを特徴とする請求項７〜１１のいずれかに記載の非水二次電池。
【請求項１３】 前記リチウム含有複合酸化物Ａを表す一般式において、ｙ＝１／６であることを特徴とする請求項７〜１２いずれかに記載の非水二次電池。
【請求項１４】 前記リチウム含有複合酸化物Ａを表す一般式において、ｙ＝１／３であることを特徴とする請求項７〜１２のいずれかに記載の非水二次電池。
【請求項１５】 前記リチウム含有複合酸化物ＡのＢＥＴ比表面積が０．３〜２ｍ 2 ／ｇであることを特徴とする請求項７〜１４のいずれかに記載の非水二次電池。
【請求項１６】 前記リチウム含有複合酸化物ＡのＮｉとＭｎの量比が１：１であることを特徴とする請求項７〜１５のいずれかに記載の非水二次電池。
[Claims]
1. The general formula Li1 + x + αNi(1-x-y + δ) / 2Mn(1-xy-δ) / 2MyO2[However, 0 ≦ x ≦ 0.05, −0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, and −0.1 ≦ δ ≦ 0.1.Because, M is represented by one or more elements selected from the group consisting of Mg, Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, and Sn], and primary particles aggregate to form secondary particles Composite oxide, the primary particles have an average particle size of 0.3 to 3 μm, and the secondary particles have an average particle size of 5 to 20 μm.And the BET specific surface area is 0.3-2 m 2 / GA lithium-containing composite oxide, characterized in that
2. The lithium-containing composite oxide according to claim 1, wherein, in the general formula, y> 0, and M is one or more elements including at least Co.
[Claim 3] In the above general formula, y = 1/6The lithium-containing composite oxide according to claim 1 or 2, wherein:
[Claim 4] The lithium-containing composite oxide according to claim 1, wherein y = 1/3 in the general formula.
[Claim 5] The lithium-containing composite oxide according to claim 1, wherein the amount ratio of Ni and Mn is 1: 1.
[Claim 6] A non-aqueous secondary battery comprising a positive electrode and a negative electrode using a lithium-containing composite oxide as an active material and a non-aqueous electrolyte, wherein the composite oxide is the lithium-containing composite oxidation according to any one of claims 1 to 5. It is characterized by being a thingNon-aqueous secondary battery.
7. A non-aqueous secondary battery comprising a positive electrode and a negative electrode using a lithium-containing composite oxide as an active material and a non-aqueous electrolyte, wherein the composite oxide includes at least a general formula Li1 + x + αNi(1-x-y + δ) / 2Mn(1-xy-δ) / 2MyO2[However, 0 ≦ x ≦ 0.05, −0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, and −0.1 ≦ δ ≦ 0.1.Because, M is represented by one or more elements selected from the group consisting of Mg, Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, and Sn], and primary particles aggregate to form secondary particles A lithium-containing composite oxide A whose secondary particles have an average particle size of 5 to 20 μm, and an average particle size smaller than the average particle size of the secondary particles of the composite oxide A. A non-aqueous secondary battery comprising a mixture of lithium-containing composite oxide B.
8. The non-aqueous secondary battery according to claim 7, wherein the proportion of the lithium-containing composite oxide B is 10 to 40% by weight of the whole positive electrode active material.
9. The average particle size of the lithium-containing composite oxide B is 3/5 or less of the average particle size of the secondary particles of the lithium-containing composite oxide A. Non-aqueous secondary battery.
10. The non-aqueous secondary oxide according to claim 7, wherein the lithium-containing composite oxide B is a composite oxide in which primary particles are aggregated to form secondary particles. battery.
11. The lithium-containing composite oxide B has the same composition as that of the lithium-containing composite oxide A or has a general formula of Li1 + a + bR1-aO2[However, 0 ≦ a ≦ 0.05, −0.05 ≦ a + b ≦ 0.05, and R is selected from the group consisting of Mg, Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, and Sn. Selected, Including at least CoThe nonaqueous secondary battery according to claim 7, wherein the nonaqueous secondary battery is represented by one or more elements.
[Claim 12] 12. The non-aqueous solution according to claim 7, wherein in the general formula representing the lithium-containing composite oxide A, y> 0 and M is one or more elements including at least Co. Secondary battery.
13. Claims The non-aqueous secondary battery according to claim 7, wherein y = 1/6 in the general formula representing the lithium-containing composite oxide A.
14. The method of claim 14 The non-aqueous secondary battery according to claim 7, wherein y = 1/3 in the general formula representing the lithium-containing composite oxide A.
15. Claims The lithium-containing composite oxide A has a BET specific surface area of 0.3 to 2 m. 2 The nonaqueous secondary battery according to claim 7, wherein the nonaqueous secondary battery is / g.
16. Claims The non-aqueous secondary battery according to claim 7, wherein the lithium-containing composite oxide A has a Ni / Mn ratio of 1: 1.
【０００９】
【課題を解決するための手段】
本発明のリチウム含有複合酸化物は、一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表され、一次粒子が凝集して二次粒子を形成した複合酸化物であり、その一次粒子の平均粒子径が０．３〜３μｍであり、二次粒子の平均粒子径が５〜２０μｍであって、ＢＥＴ比表面積が０．３〜２ｍ 2 ／ｇであることを特徴とする。
[0009]
[Means for Solving the Problems]
Lithium-containing composite oxide of the present invention have the general formula Li 1 + x + α Ni ( 1-xy + δ) / 2 Mn (1-xy-δ) / 2 M y O 2 [ however, 0 ≦ x ≦ 0.05, −0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, −0.1 ≦ δ ≦ 0.1 , and M is Mg, Ti, Cr, Fe, 1 or more elements selected from the group consisting of Co, Cu, Zn, Al, Ge, and Sn], and a composite oxide in which primary particles aggregate to form secondary particles. The average particle diameter is 0.3 to 3 μm, the average particle diameter of secondary particles is 5 to 20 μm , and the BET specific surface area is 0.3 to 2 m 2 / g .
さらに本発明の非水二次電池は、一般式Ｌｉ 1+x+α Ｎｉ (1-x-y+δ)/2 Ｍｎ (1-x-y-δ)/2 Ｍ y Ｏ 2 ［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表され、一次粒子が凝集して二次粒子を形成した複合酸化物であり、その二次粒子の平均粒子径が５〜２０μｍであるリチウム含有複合酸化物をＡとしたときに、正極活物質として、少なくとも、リチウム含有複合酸化物Ａと、その平均粒子径が前記複合酸化物Ａの二次粒子の平均粒子径よりも小さいリチウム含有複合酸化物Ｂとを混合して用いることを好ましい態様とするものである。 Further non-aqueous secondary battery of the present invention have the general formula Li 1 + x + α Ni ( 1-xy + δ) / 2 Mn (1-xy-δ) / 2 M y O 2 [ however, 0 ≦ x ≦ 0.05, −0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, −0.1 ≦ δ ≦ 0.1, and M is Mg, Ti, Cr, Fe 1 or more elements selected from the group consisting of Co, Cu, Zn, Al, Ge, and Sn], and the secondary particles are aggregated to form secondary particles. When the lithium-containing composite oxide having an average particle diameter of 5 to 20 μm is A, the positive electrode active material is at least lithium-containing composite oxide A and the average particle diameter of the composite oxide A It is preferable to use a mixture of lithium-containing composite oxide B smaller than the average particle size of the secondary particles.
【００１２】
【発明の実施の形態】
以下、発明の実施の形態により、本発明をより具体的に説明する。本発明のリチウム含有複合酸化物は、一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表され、一次粒子が凝集して二次粒子を形成した複合酸化物であり、その一次粒子の平均粒子径が０．３〜３μｍであり、二次粒子の平均粒子径が５〜２０μｍであって、ＢＥＴ比表面積が０．３〜２ｍ 2 ／ｇであることを特徴とする。
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to embodiments of the invention. Lithium-containing composite oxide of the present invention have the general formula Li 1 + x + α Ni ( 1-xy + δ) / 2 Mn (1-xy-δ) / 2 M y O 2 [ however, 0 ≦ x ≦ 0.05, −0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, −0.1 ≦ δ ≦ 0.1 , and M is Mg, Ti, Cr, Fe, 1 or more elements selected from the group consisting of Co, Cu, Zn, Al, Ge, and Sn], and a composite oxide in which primary particles aggregate to form secondary particles. The average particle diameter is 0.3 to 3 μm, the average particle diameter of secondary particles is 5 to 20 μm , and the BET specific surface area is 0.3 to 2 m 2 / g .
本発明において、上記のような限られた組成範囲のみが選択されるのは以下の理由による。すなわち、ＮｉおよびＭｎを有する層状のリチウム含有複合酸化物においては、ＮｉとＭｎの量比が１：１となる一般式ＬｉＮｉ1/2Ｍｎ1/2Ｏ2で表される組成を基本として、ＮｉおよびＭｎがそれぞれｘ／２ずつＬｉで置換され、ＮｉとＭｎの量比が１／２からそれぞれδ／２および−δ／２だけずれ、Ｌｉの量比がαだけ幅を有し、かつ、ＮｉおよびＭｎが、それぞれｙ／２ずつ元素Ｍ（ただしＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎより選択される１種以上の元素）で置換された組成、すなわち、一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］で表される組成範囲において、その結晶構造が安定化され、４Ｖ付近の電位領域での充放電の可逆性や充放電サイクルに対する耐久性に優れた複合酸化物が得られることによる。 In the present invention, only the limited composition range as described above is selected for the following reason. That is, in the layered lithium-containing composite oxide having Ni and Mn, based on the composition represented by the general formula LiNi 1/2 Mn 1/2 O 2 in which the quantity ratio of Ni and Mn is 1: 1, Ni and Mn are each replaced by x / 2 with Li, the quantity ratio of Ni and Mn is shifted from ½ by δ / 2 and −δ / 2 respectively, the quantity ratio of Li has a width by α, and , Ni, and Mn are each replaced by y / 2 elements M (where M is one or more elements selected from Mg, Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, Sn) composition, i.e., the general formula Li 1 + x + α Ni ( 1-xy + δ) / 2 Mn (1-xy-δ) / 2 M y O 2 [ however, 0 ≦ x ≦ 0.05, - 0.05 ≦ x + a α ≦ 0.05,0 ≦ y ≦ 0.4, a -0.1 ≦ δ ≦ 0.1, M is Mg, Ti, Cr, Fe, Co In the composition range represented by one or more elements selected from the group consisting of Cu, Zn, Al, Ge, and Sn], the crystal structure is stabilized, and the reversibility of charge and discharge in a potential region near 4 V This is because a composite oxide having excellent durability against charge and discharge cycles is obtained.
上記一般式Ｌｉ1+x+αＮｉ(1-x-y+δ)/2Ｍｎ(1-x-y-δ)/2ＭyＯ2［ただし、０≦ｘ≦０．０５、−０．０５≦ｘ＋α≦０．０５、０≦ｙ≦０．４であり、−０．１≦δ≦０．１であって、ＭはＭｇ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｇｅ、Ｓｎからなる群から選択された１種以上の元素］において、ＮｉとＭｎの量比は基本的には１：１であることを必要とし、中央値からのずれ（δ／２）は、−０．１≦δ≦０．１と小さい値しか許容されない。ただし、０．２＜ｙ≦０．４の組成範囲では、結晶構造の安定性がより高くなり、単一相が形成されやすくなるため、上記ずれが大きくなっても目的とする複合酸化物を得ることができる。このため、上記一般式において、δのとり得る範囲は、基本的には−０．１≦δ≦０．１と狭いのであるが、０．２＜ｙ≦０．４の組成範囲では、δの値を−０．２４≦δ≦０．２４の範囲まで拡張してもよい。 The general formula Li 1 + x + α Ni ( 1-xy + δ) / 2 Mn (1-xy-δ) / 2 M y O 2 [ however, 0 ≦ x ≦ 0.05, -0.05 ≦ x + α ≦ 0.05, 0 ≦ y ≦ 0.4, −0.1 ≦ δ ≦ 0.1 , and M is Mg, Ti, Cr, Fe, Co, Cu, Zn, Al, Ge , One or more elements selected from the group consisting of Sn], the amount ratio of Ni and Mn basically needs to be 1: 1, and the deviation from the median (δ / 2) is Only a small value of −0.1 ≦ δ ≦ 0.1 is allowed. However, in the composition range of 0.2 <y ≦ 0.4, the crystal structure becomes more stable and a single phase is easily formed. Can be obtained. Therefore, in the above general formula, the possible range of δ is basically as narrow as −0.1 ≦ δ ≦ 0.1, but in the composition range of 0.2 <y ≦ 0.4, δ May be extended to a range of −0.24 ≦ δ ≦ 0.24.
また、上記組成を有する複合酸化物の形態として、一次粒子が凝集して二次粒子を形成したもので、二次粒子の平均粒子径が５〜２０μｍである複合酸化物が選択される。これは、一次粒子が凝集して二次粒子を形成したものにおいて、充放電における反応性や複合酸化物の充填性を高めることができるからであり、一次粒子の平均粒子径を０．３〜３μｍとすることにより、充放電における反応性を高めて電池の負荷特性を向上させることができ、二次粒子の平均粒子径を５〜２０μｍとすることにより、複合酸化物の充填性を高めて電極を高容量化することができる。 Moreover, as a form of the composite oxide having the above composition, a composite oxide in which primary particles are aggregated to form secondary particles, and the average particle diameter of the secondary particles is 5 to 20 μm is selected. This is because primary particles agglomerate to form secondary particles, so that the reactivity in charge and discharge and the filling property of the composite oxide can be improved. By setting it to 3 μm, it is possible to improve the load characteristics of the battery by increasing the charge / discharge reactivity, and by increasing the average particle size of the secondary particles to 5 to 20 μm, the filling property of the composite oxide is increased. The capacity of the electrode can be increased.
上述した粒子形態のリチウム含有複合酸化物は、例えば、ＮｉおよびＭｎ、またはＮｉ、Ｍｎおよび元素Ｍの塩を溶解した水溶液をアルカリ水溶液中に投入し、ＮｉおよびＭｎまたはＮｉ、Ｍｎおよび元素Ｍの共沈水酸化物を合成し、これをリチウム化合物とともに焼成し、さらに必要に応じて合成された複合酸化物を機械的に粉砕およびふるい分けすることにより得ることができる。焼成は、空気中あるいは酸素ガス中など酸素を１０体積％以上含む雰囲気中で行うことが望ましく、焼成温度はおよそ７００℃〜１１００℃で、焼成時間は１〜２４時間とするのが一般的である。また、上記焼成処理の前に、焼成温度よりも低い温度（およそ２５０〜８５０℃）で０．５〜３０時間程度予備加熱を行い、さらに上記焼成処理を行うようにすれば、複合酸化物の均質化が促進されるので好ましい。ここで、複合酸化物の一次粒子径は、予備加熱あるいは焼成の温度およびその処理時間を調整することにより制御することができ、二次粒子径は、機械的な粉砕の程度およびふるい分けにより制御することができる。 In the lithium-containing composite oxide in the form of particles described above, for example, an aqueous solution in which Ni and Mn, or a salt of Ni, Mn, and element M are dissolved is put into an alkaline aqueous solution, and Ni and Mn or Ni, Mn, and element M are mixed. It can be obtained by synthesizing a coprecipitated hydroxide, calcining it with a lithium compound, and mechanically grinding and sieving the synthesized composite oxide as necessary. Firing is preferably performed in an atmosphere containing 10% by volume or more of oxygen, such as in air or oxygen gas. The firing temperature is approximately 700 ° C. to 1100 ° C., and the firing time is generally 1 to 24 hours. is there. Further, prior to the firing treatment, preheating is performed at a temperature lower than the firing temperature (approximately 250 to 850 ° C.) for about 0.5 to 30 hours, and further the firing treatment is performed. This is preferable because homogenization is promoted. Here, the primary particle size of the composite oxide can be controlled by adjusting the preheating or firing temperature and the treatment time, and the secondary particle size is controlled by the degree of mechanical grinding and sieving. be able to.
なお、上記リチウム含有複合酸化物は、単独で正極活物質として用いることができるが、この場合は、その一次粒子の平均粒子径が０．３〜３μｍである複合酸化物が選択される。また、二次粒子の平均粒子径が５〜２０μｍである前記リチウム含有複合酸化物（以下、リチウム含有複合酸化物Ａとする）と、これよりも平均粒子径の小さいリチウム含有複合酸化物（以下、リチウム含有複合酸化物Ｂとする）とを混合して用いることにより、活物質の充填性が一層向上し、電極の容量を高めることができる。これは、平均粒子径の小さいリチウム含有複合酸化物Ｂが、リチウム含有複合酸化物Ａの粒子間の空隙に入りこむことにより、正極合剤の密度が大きくなるからである。 In addition, although the said lithium containing complex oxide can be used independently as a positive electrode active material , the complex oxide whose average particle diameter of the primary particle is 0.3-3 micrometers is selected in this case. Further, the lithium-containing composite oxide average particle diameter of the secondary particles is 5 to 20 [mu] m (hereinafter, the lithium-containing complex oxide A) and which average less lithium-containing composite oxide particle diameter (hereinafter than And the lithium-containing composite oxide B) are used in combination, whereby the fillability of the active material can be further improved and the capacity of the electrode can be increased. This is because the density of the positive electrode mixture is increased when the lithium-containing composite oxide B having a small average particle diameter enters the voids between the particles of the lithium-containing composite oxide A.
（実施例３〜６および比較例１〜３）
焼成温度および焼成時間を変えて複合酸化物の合成を行い、合成した複合酸化物を粉砕しさらにふるい分けすることにより、表１に示すリチウム含有複合酸化物を得た。なお、実施例５では、共沈水酸化物としてＮｉ、ＭｎおよびＣｏを５：５：２の割合（ｙ＝１／６）で含有する水酸化物を用い、実施例６では、Ｎｉ、ＭｎおよびＣｏを１：１：１の割合（ｙ＝１／３）で含有する水酸化物を用いた。
(Examples 3-6 and Comparative Examples 1-3)
The composite oxide was synthesized by changing the firing temperature and firing time, and the composite oxide thus synthesized was pulverized and further sieved to obtain lithium-containing composite oxides shown in Table 1. In Example 5, a hydroxide containing Ni, Mn and Co in a ratio of 5: 5: 2 (y = 1/6 ) was used as the coprecipitated hydroxide. In Example 6, Ni, Mn and Co A hydroxide containing Co at a ratio of 1: 1: 1 (y = 1/3) was used.
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