Thermodynamically Driven Synthetic Optimization for Cation‐Disordered Rock Salt Cathodes

Abstract Relating the synthesis conditions of materials to their functional performance has long been an experience‐based trial‐and‐error process. However, this methodology is not always efficient in identifying an appropriate protocol and can lead to overlooked opportunities for the performance optimization of materials through simple modifications of the synthesis process. In this work, the authors systematically track the structural evolution in the synthesis of a representative disordered rock salt (a promising next‐generation Li‐ion cathode material) at the scale of both the long‐range crystal structure and the short‐range atomic structure using various in situ and ex situ techniques, including transmission electron microscopy, X‐ray diffraction, and pair distribution function analysis. An optimization strategy is proposed for the synthesis protocol, leading to a remarkably enhanced capacity (specific energy) of 313 mAh g −1 (987 Wh kg −1 ) at a low rate (20 mA g −1 ), with a capacity of more than 140 mAh g −1 retained even at a very high cycling rate of 2000 mA g −1 . This strategy is further rationalized using ab initio calculations, and important opportunities for synthetic optimization demonstrated in this study are highlighted.