Origin of oxygen-redox and transition metals dissolution in Ni-rich LixNi0.8Co0.1Mn0.1O2 cathode

Recently, Ni-rich LiNi_xCo_yMn_1-x-yO₂ (x ≥ 0.8) draw significant research attention as cathode materials in lithium-ion batteries due to their superiority in energy density. However, the oxygen release and the transition metals (TMs) dissolution during the (dis)charging process lead to serious safety issues and capacity loss, which highly prevent its application. In this work, we systematically explored the stability of lattice oxygen and TM sites in LiNi_0.8Co_0.1Mn_0.1O₂(NCM811) cathode via investigating various vacancy formations during lithiation/delithiation, and properties such as the number of unpaired spins (NUS), net charges, and d band center were comprehensively studied. In the process of delithiation (x = 1 → 0.75 → 0), the vacancy formation energy of lattice oxygen [E_vac(O)] has been identified to follow the order of E_vac(O-Mn) > E_vac(O-Co) > E_vac(O-Ni), and E_vac(TMs) shows a consistent trend with the sequence of E_vac(Mn) > E_vac(Co) > E_vac(Ni), demonstrating the importance of Mn to stabilize the structural skeleton. Furthermore, the |NUS| and net charge are proved to be good descriptors for measuring E_vac(O/TMs), which show linear correlations with E_vac(O) and E_vac(TMs), respectively. Li vacancy plays a pivotal role on E_vac(O/TMs). E_vac(O/TMs) at x = 0.75 vary extremely between the NiCoMnO layer (NCM layer) and the NiO layer (Ni layer), which correlates well with |NUS| and net charge in the NCM layer but aggregates in a small region in the Ni layer due to the effect of Li vacancies. In general, this work provides an in-depth understanding of the instability of lattice oxygen and transition metal sites on the (104) surface of Ni-rich NCM811, which might give new insights into oxygen release and transition metal dissolution in this system.