Origin and Regulation of Interface Fusion during Synthesis of Single‐Crystal Ni‐Rich Cathodes

Abstract Interface fusion plays a key role in constructing Ni‐based single‐crystal cathodes, and is governed by the atomic migration related to kinetics. However, the interfacial atom migration path and its control factors are lack of clearly understanding. Herein, we systematically probe the solid‐state synthesis mechanism of single‐crystal LiNi 0.92 Co 0.04 Mn 0.04 O 2 , including the effects of precursor size, Li/transition metal (TM) ratio and sintering temperature on the structure. Multi‐dimensional analysis unravels that thermodynamics drives interface atoms migration through intermediate state (i.e., cation mixing phase) to induce grain boundary fusion. Moreover, we demonstrate that smaller precursor size (<6 μm), lager Li/TM ratio (>1.0) and higher temperature (≥810 °C) are conducive to promote the growth of the intermediate state due to reaction kinetics enhancement, and ultimately strengthen the atomic migration‐induced interface fusion.