Lithium vanadium phosphate Li 3 V 2 (PO 4 ) 3 (LVP) has emerged as an appealing cathode material for next generation lithium-ion batteries owing to its high theoretical capacity (197 mAh g -1 ) and high average working potential around 4.0 V vs Li/Li + . However, capacity fading problem limits its practical application, especially when high cut-off voltage over 4.3 V is applied. In this study, the capacity fading mechanisms of LVP in different voltage windows 3.0 -4.3 V and 3.0 -4.8 V are studied systematically by using electrochemical impedance spectroscopy, galvanostatic intermittent titration technique, cyclic voltammetry, and in-situ X-ray absorption spectroscopy. Surprisingly, the structure of LVP can be fully recovered after one cycle (even for a cut-off voltage as high as 4.8 V). It indicates that LVP is a promising cathode system with excellent structure reversibility intrinsically. We revealed that the capacity fading during high voltage cycling is mainly due to parasitic reaction with the electrolyte, kinetics limitation and V dissolution, rather than LVP structure degradation. In addition, A "crystalline-2 amorphous-crystalline" phase transition pathway was revealed during LVP synthesis process of solidstate reaction by using synchrotron based in-situ X-ray diffraction.
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