Remarkably Improved Electrochemical Performance of Li- and Mn-Rich Cathodes upon Substitution of Mn with Ni.
Li- and Mn-rich transition-metal oxides of layered structure are promising cathodes for Li-ion batteries because of their high capacity values, ≥250 mAh g-1. These cathodes suffer from capacity fading and discharge voltage decay upon prolonged cycling to potential higher than 4.5 V. Most of these Li- and Mn-rich cathodes contain Ni in a 2+ oxidation state. The fine details of the composition of these materials may be critically important in determining their performance. In the present study, we used Li1.2Ni0.13Mn0.54Co0.13O2as the reference cathode composition in which Mn ions are substituted by Ni ions so that their average oxidation state in Li1.2Ni0.27Mn0.4Co0.13O2could change from 2+ to 3+. Upon substitution of Mn with Ni, the specific capacity decreases but, in turn, an impressive stability was gained, about 95% capacity retention after 150 cycles, compared to 77% capacity retention for Li1.2Ni0.13Mn0.54Co0.13O2cathodes when cycled at a C/5 rate. Also, a higher average discharge voltage of 3.7 V is obtained for Li1.2Ni0.27Mn0.4Co0.13O2cathodes, which decreases to 3.5 V after 150 cycles, while the voltage fading of cathodes comprising the reference material is more pronounced. The Li1.2Ni0.27Mn0.4Co0.13O2cathodes also demonstrate higher rate capability compared to the reference Li1.2Ni0.13Mn0.54Co0.13O2cathodes. These results clearly indicate the importance of the fine composition of cathode materials containing the five elements Li, Mn, Ni, Co, and O. The present study should encourage rigorous optimization efforts related to the fine composition of these cathode materials, before external means such as doping and coating are applied.
Prasant
P
Kumar Nayak
Judith
J
Grinblat
Elena
E
Levi
Tirupathi Rao
TR
Penki
Mikhael
M
Levi
Department of Energy Engineering, Hanyang University , Seoul 133-791, Republic of Korea.
Yang-Kook
YK
Sun
Boris
B
Markovsky
Doron
D
Aurbach
Li- and Mn-rich cathodes; Li-ion batteries; Mn substitution by Ni; impedance; voltage stabilization