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Published on: November 10, 2014
Rate-dependent, Li-ion insertion/deinsertion behavior of LiFePO4 cathodes in commercial 18650 LiFePO4 cells
1Department of Mechanical Engineering, Purdue School of Engineering and Technology, Indiana University-Purdue University , Indianapolis, Indiana 46202, United States.
Abstract:
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.
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