Phase Transition Analysis between LiFePO₄and FePO₄by In-Situ Time-Resolved X-ray Absorption and X-ray Diffraction

In-situ time-resolved X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) are applied to investigate the phase transition mechanism between LiFePO 4 and FePO 4 . Phase formation kinetics is discussed by using the phase fractions of LiFePO 4 and FePO 4 directly obtained from the XRD measurement and the amount of the passed current synchronized by the XRD measurement with Kolmogorov-Johnson-Mehl-Avrami (KJMA) analysis. For both of the lithium extraction and insertion process, the KJMA analysis from the XRD and amount of the passed current data indicate that the phase formation of LiFePO 4 and FePO 4 proceeds via one-dimensional phase boundary movement. For the lithium extraction process, the two phase coexistence of LiFePO 4 and FePO 4 is observed under the potential step conditions, and the KJMA plot based on the passed current data is relatively in good agreement with the one based on the XRD data. On the other hand, for the lithium insertion process, considerable peak boarding which implies intermediate state formation during the phase transition occurs, and the LiFePO 4 phase formation is delayed compared with the amount of the passed current, especially in the case of small particle size. These results indicate that the phase transition behavior during lithium insertion is different from that of the typical two phase reaction.