Role of Substitution Elements in Enhancing the Structural Stability of Li-Rich Layered Cathodes.

Element doping/substitution has been recognized as an effective strategy to enhance the structural stability of layered cathodes. However, abundant substitution studies not only lack a clear identification of the substitution sites in the material lattice, but the rigid interpretation of the transition metal (TM)-O covalent theory is also not sufficiently convincing, resulting in the doping/substitution proposals being dragged into design blindness. In this work, taking Li 1.2 Ni 0.2 Mn 0.6 O 2 as a prototype, the intense correlation between the "disordered degree" (Li/Ni mixing) and interface-structure stability (e.g., TM-O environment, slab/lattice, and Li + reversibility) is revealed. Specifically, the degree of disorder induced by the Mg/Ti substitution extends in the opposite direction, conducive to sharp differences in the stability of TM-O, Li + diffusion, and anion redox reversibility, delivering fairly distinct electrochemical performance. Based on the established paradigm of systematic characterization/analysis, the "degree of disorder" has been shown to be a powerful indicator of material modification by element substitution/doping.