Revisiting Cationic Doping Impacts in Ni-Rich Cathodes
Xueyan Hou, Takuya Katsumata, Yuta Kimura, Y. Tamenori, Kiyofumi Nitta, Hirona Yamagishi, Koji Amezawa, Takashi Nakamura
Abstract
As a promising cathode material for high-energy-density Li-ion batteries, Ni-rich layered oxide cathode active materials deliver high specific capacity. However, their electrochemical performance degrades rapidly upon charge/discharge cycles probably due to electrochemical/thermochemical instabilities. While cationic doping in the transition-metal site has been regarded as an effective strategy to enhance the electrochemical performance, the true impact of cation doping is not well understood. To quantitatively assess the impact of cationic doping, in this work, the electrochemical performance and lattice oxygen stability of LiNi 0.82 Co 0.18 O 2, isovalent Al 3+ -doped LiNi 0.82 Co 0.15 Al 0.03 O 2, and high-valent Ti 4+ -doped LiNi 0.82 Co 0.15 Ti 0.03 O 2 were investigated. Despite significant improvements in electrochemical performance by Al 3+ and Ti 4+ doping, it was revealed that these cation dopings had no discernible effect on the lattice oxygen stability. Such information suggests that the electrochemical enhancement by Al 3+ /Ti 4+ doping is not attributed to the stabilization of lattice oxygen. This work highlights the importance of independent and quantitative experimental evaluations on kinetic electrochemical properties and thermodynamic stability of lattice oxygen to establish rational guidelines for doping strategy toward high-energy-density and reliable cathode-active materials.