Beyond Constant Current: Origin of Pulse-Induced Activation in Phase-Transforming Battery Electrodes

Mechanistic understanding of phase transformation dynamics during battery charging and discharging is crucial toward rationally improving intercalation electrodes. Most studies focus on constant-current conditions. However, in real battery operation, such as in electric vehicles during discharge, the current is rarely constant. In this work we study current pulsing in LiFePO₄ (LFP), a model and technologically important phase-transforming electrode. A current-pulse activation effect has been observed in LFP, which decreases the overpotential by up to ∼70% after a short, high-rate pulse. This effect persists for hours or even days. Using scanning transmission X-ray microscopy and operando X-ray diffraction, we link this long-lived activation effect to a pulse-induced electrode homogenization on both the intra- and interparticle length scales, i.e., within and between particles. Many-particle phase-field simulations explain how such pulse-induced homogeneity contributes to the decreased electrode overpotential. Specifically, we correlate the extent and duration of this activation to lithium surface diffusivity and the magnitude of the current pulse. This work directly links the transient electrode-level electrochemistry to the underlying phase transformation and explains the critical effect of current pulses on phase separation, with significant implication on both battery round-trip efficiency and cycle life. More broadly, the mechanisms revealed here likely extend to other phase-separating electrodes, such as graphite.