Solid‐State Reaction Heterogeneity During Calcination of Lithium‐Ion Battery Cathode

During solid‐state calcination, with increasing temperature, materials undergo complex phase transitions with heterogeneous solid‐state reactions and mass transport. Precise control of the calcination chemistry is therefore crucial for synthesizing state‐of‐the‐art Ni‐rich layered oxides (LiNi1‐x‐yCoxMnyO2, NRNCM) as cathode materials for lithium‐ion batteries. Although the battery performance depends on the chemical heterogeneity during NRNCM calcination, it has not yet been elucidated. Herein, through synchrotron‐based X‐ray, mass spectrometry microscopy, and structural analyses, it is revealed that the temperature‐dependent reaction kinetics, the diffusivity of solid‐state lithium sources, and the ambient oxygen control the local chemical compositions of the reaction intermediates within a calcined particle. Additionally, it is found that the variations in the reducing power of the transition metals (i.e., Ni, Co, and Mn) determine the local structures at the nanoscale. The investigation of the reaction mechanism via imaging analysis provides valuable information for tuning the calcination chemistry and developing high‐energy/power density lithium‐ion batteries. High‐temperature calcination used for Li‐ion battery particle synthesis is chemically imaged. Various parallel and serial combinations of heterogeneous reactions, such as the thermal aerobic/anaerobic decomposition, Li2CO3 decomposition, Li2‐O insertion/diffusion, and O2 insertion/diffusion, prevail during the calcination reaction. The anaerobic decomposition of the precursor core slows down Li2‐O incorporation.