Fundamental Insights into Cathode Stability: Linking Compositional Tuning and Local Coordination in Complex Metal Oxides under Aqueous Transformations

Compositional tuning of complex metal oxides in Li-ion battery materials influences their performance as well as their end-of-life behavior, in particular, the tendency to release toxic metal cations in aqueous solution. We modeled ternary variants of a parent LiCoO2 delafossite structure by varying the metal identity and relative amounts. This yielded ten model formulations of Li(A4/6B1/6C1/6)O2, where the material is enriched with the A metal and doped with B and C, with Ni, Mn, Co, Fe, Al, V, and Ti as constituent metals. To assess their stability in aqueous conditions, metal release energetics were calculated using a combination of Density Functional Theory calculations and thermodynamics. Metal release in ternary oxides is dictated by subtle variations in the coordination environment of the leaving group. To identify governing chemical features across diverse compositions with varying local coordination environments, we leverage random forest regression and descriptor importance analysis. A key result is that metal–oxygen orbital hybridization, quantified using a projected density-of-states-derived descriptor, Hd/p, provides a physically grounded measure of interaction strength that governs metal release energetics. This refined perspective goes beyond conventional oxidation state considerations and offers more robust insights for materials science. Finally, we model defect surface-bound O2 dimer formation as a proxy for reactive oxygen species (ROS) generation. The results show that Ni-rich compositions more readily stabilize spin-polarized O2 dimers, corroborating experimental reports of an increased ROS-driven biological response. Our results establish a compositional and electronic basis for metal release and surface oxygen reactivity that form a rationale for complex metal oxide design principles.