Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dVdxLi) is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (∼4.5–4.7 V). In this study, we develop a lattice model based on first principles to understand and quantify the voltage slope of cation-disordered LiMO2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of high-voltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disor...

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