Phase transition analysis between LiFePO₄ and FePO₄ by in-situ time-resolved X-ray absorption and X-ray diffraction

In-situ time-resolved X-ray absorption spectroscopy (XAS) andX-ray diffraction (XRD) are applied to investigate the phase transition mechanism between LiFePO₄ and FePO₄. Phase formation kinetics is discussed by using the phase fractions of LiFePO₄ 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 LiFePO₄ and FePO₄ proceeds via onedimensional phase boundary movement. For the lithium extraction process, the two phase coexistence of LiFePO₄ and FePO₄ 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 LiFePO₄ 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.