Synthesis and electrochemical properties of layered $Li[Ni_xCo_{1-2x}Mn_x]O_2$ materials for lithium secondary batteries prepared by mechanical alloying

기계적 합금법을 이용한 리튬 2차 전지용 층상 양극물질 $Li[Ni_xCo_{1-2x}Mn_x]O_2$ 의 합성 및 전기화학적 특성에 관한 연구

The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).