In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO2 from Hydroxides

Calcination is a solid‐state synthesis process widely deployed in battery cathode manufacturing. However, its inherent complexity associated with elusive intermediates hinders the predictive synthesis of high‐performance cathode materials. Here, correlative in situ X‐ray absorption/scattering spectroscopy is used to investigate the calcination of nickel‐based cathodes, focusing specifically on the archetypal LiNiO2 from Ni(OH)2. Combining in situ observation with data‐driven analysis reveals concurrent lithiation and dehydration of Ni(OH)2 and consequently, the low‐temperature crystallization of layered LiNiO2 alongside lithiated rocksalts. Following early nucleation, LiNiO2 undergoes sluggish crystallization and structural ordering while depleting rocksalts; ultimately, it turns into a structurally‐ordered layered phase upon full lithiation but remains small in size. Subsequent high‐temperature sintering induces rapid crystal growth, accompanied by undesired delithiation and structural degradation. These observations are further corroborated by mesoscale modeling, emphasizing that, even though calcination is thermally driven and favors transformation towards thermodynamically equilibrium phases, the actual phase propagation and crystallization can be kinetically tuned via lithiation, providing freedom for structural and morphological control during cathode calcination. Calcination is a commonly used in making battery cathode materials. However, its inherent complexity associated with elusive intermediates hinders the predictive synthesis of high‐performance cathodes. This study unveils the kinetic crystallization process of forming LiNiO2, the archetypical Ni‐based cathode during calcination from hydroxides, providing insights into controlling structure and morphology through lithiation in the calcination process.