Accelerating the Electrochemical Formation of the δ Phase in Manganese‐Rich Rocksalt Cathodes

Abstract Mn‐rich disordered rocksalt materials with Li‐excess (DRX) materials have emerged as a promising class of earth‐abundant and energy‐dense next‐generation cathode materials for lithium‐ion batteries. Recently, an electrochemical transformation to a spinel‐like “δ” phase has been reported in Mn‐rich DRX materials, with improved capacity, rate capability, and cycling stability compared with previous DRX compositions. However, this transformation unfolds slowly over the course of cycling, complicating the development and understanding of these materials. In this work, it is reported that the transformation of Mn‐rich DRX materials to the promising δ phase can be promoted to occur much more rapidly by electrochemical pulsing at elevated temperature, rate, and voltage. To extend this concept, micron‐sized single‐crystal DRX particles are also transformed to the δ phase by the same method, possessing greatly improved cycling stability in the first demonstration of cycling for large, single‐crystal DRX particles. To shed light on the formation and specific structure of the δ phase, X‐ray diffraction, scanning electron nanodiffraction (SEND) and atomic resolution STEM‐HAADF are used to reveal a nanodomain spinel structure with minimal remnant disorder.