Predicting Morphological Evolution during Coprecipitation of MnCO3 Battery Cathode Precursors Using Multiscale Simulations Aided by Targeted Synthesis

The performance of lithium-ion batteries is intimately linked to both the structure and the morphology of the cathode material, which in turn is critically linked to the synthesis conditions. However, few studies focus on understanding synthesis, especially during the coprecipitation of metal oxide precursors, a process that largely determines the final morphology of the material. In this paper, we go beyond the typical equilibrium particle shape analysis conducted in the literature and incorporate kinetic aspects of morphology evolution. We perform these studies using controlled synthesis on a well-defined metal salt system (MnCO₃) combined with multiscale simulations and high-resolution microscopy. Results show that with increasing metal concentration, the particles transition from rhombohedral to cubic to spherical shapes. Computational analysis using density functional theory (DFT) reveals that rhombohedral shaped particles evolve under equilibrium conditions. Phase field techniques indicate that at higher metal concentrations, fast growth kinetics of the precipitates result in the transition to cubic and, subsequently, spherical shapes, accompanied by a decrease in particle size. This study, while limited to the one metal salt system, provides an approach to shed light on the synthesis process of mixed transition metal salts, gradient materials, and other cathode materials of interest to the battery community.