Rate-Dependent, Li-Ion Insertion/Deinsertion Behavior of LiFePO₄ Cathodes in Commercial 18650 LiFePO₄ Cells

We have performed operando synchrotron high-energy X-ray diffraction (XRD) to obtain nonintrusive, real-time monitoring of the dynamic chemical and structural changes in commercial 18650 LiFePO4/C cells under realistic cycling conditions. The results indicate a nonequilibrium lithium insertion and extraction in the LiFePO4 cathode, with neither the LiFePO4 phase nor the FePO4 phase maintaining a static composition during lithium insertion/extraction. On the basis of our observations, we propose that the LiFePO4 cathode simultaneously experiences both a two-phase reaction mechanism and a dual-phase solid-solution reaction mechanism over the entire range of the flat voltage plateau, with this dual-phase solid-solution behavior being strongly dependent on charge/discharge rates. The proposed dual-phase solid-solution mechanism may explain the remarkable rate capability of LiFePO4 in commercial cells.