Affiliation:
1. National Synchrotron Light Source II Brookhaven National Laboratory Upton NY 11973 USA
2. Argonne National Laboratory Lemont IL 60439 USA
3. Joint Photon Sciences Institute Stony Brook University Stony Brook NY 11794 USA
Abstract
AbstractCalcination 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.
Funder
Argonne National Laboratory
Office of Science
Brookhaven National Laboratory
Vehicle Technologies Program
Cited by
5 articles.
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