Microscale Li[Li0.19Ni0.16Co0.08Mn0.57]O2 powders with a high tap density were synthesized using [Ni0.2Co0.1Mn0.7]O x precursor with a unique microstructure via coprecipitation in flowing air. The synthesized Li[Li0.19Ni0.16Co0.08Mn0.57]O2 powders were composed of spherical nanosized primary particles, which results in a high tap density due to the high packing of the spherical primary particles. When used as electrode in a lithium cell, Li[Li0.19Ni0.16Co0.08Mn0.57]O2 exhibits a very high gravimetric capacity of 263mAhg−1 and a volumetric capacity of 956mAhcm−3, as well as an excellent rate capability delivering a discharge capacity of 202mAhg−1 at a 2C-rate. TEM analysis together with SEM observations show that the electrochemical performance of the Li[Li0.19Ni0.16Co0.08Mn0.57]O2 electrode is primarily governed by its microstructure.