Correlating the phase evolution and anionic redox in Co-Free Ni-Rich layered oxide cathodes

Abstract Current trend of high-capacity Ni-rich layered cathode is to develop high-Ni and low-Co or Co-free oxides. The high Ni content layered oxides provide great advantages in capacity, cost and environmental benignity, similar to LiNiO2 parent compound. But they also inherit drawbacks in structural and chemical instability at high voltages upon cycling. Elemental substitution plays a profound role in addressing these challenges. This work elucidates the roles of Al doping in cationic redox and anionic oxygen activity in LiAlxNi1-xO2 using combined X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) as well as operando differential electrochemical mass spectrometry (DEMS). Using synchrotron wide-angle X-ray scattering (WAXS), we extrapolate a general principle of phase transition and its coupling with lattice anionic oxygen redox. These findings shed light on the advancement of high-capacity, stable-cycling and safe-operating Ni-rich cathode materials for next generation Li-ion batteries.