Many compounds used as battery storage electrodes undergo large composition changes during use that are accompanied by a first-order phase transition. Most studies of these phase transitions have focused on the unit cell to single-crystallite scale, whereas real battery electrodes are typically composed of mesoscopic assemblies of nanocrystallites, for which phase transformation mechanisms are poorly understood. In this work, a systematic study is conducted of the potentiostatic (constant driving force) kinetics of phase transition in secondary particles of representative intercalation compounds: LiFePO4, LiMn1–xFexPO4, and Li4Ti5O7. Storage kinetics are studied as a function of overpotential, material composition, primary particle size, and temperature. We find that in regimes where phase transformation occurs, the results can be self-consistently explained as nucleation and growth kinetics within the framework of the Johnson–Mehl–Avrami–Kolmogorov model. This implies that despite the common secondary particle topology, the electrochemically driven phase transformations occur by nucleation and growth with little apparent resistance to phase propagation across the grain boundaries. Growth appears to be one-dimensional in nature, consistent with a hybrid growth model in which rapid surface propagation is followed by slower growth into particles.
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