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Vanadium phosphate positive electrode materials attract great interest in the field of Alkali-ion (Li, Na and K-ion) batteries due to their ability to store several electrons per transition metal. These multi-electron reactions (from V2+ to V5+) combined with the high voltage of corresponding redox couples (e.g., 4.0 V vs. for V3+/V4+ in Na3V2(PO4)(2)F-3) could allow the achievement the 1 kWh/kg milestone at the positive electrode level in Alkali-ion batteries. However, a massive divergence in the voltage reported for the V3+/V4+ and V4+/V5+ redox couples as a function of crystal structure is noticed. Moreover, vanadium phosphates that operate at high V3+/V4+ voltages are usually unable to reversibly exchange several electrons in a narrow enough voltage range. Here, through the review of redox mechanisms and structural evolutions upon electrochemical operation of selected widely studied materials, we identify the crystallographic origin of this trend: the distribution of PO4 groups around vanadium octahedra, that allows or prevents the formation of the vanadyl distortion ((OV4+)-V- horizontal ellipsis =O or (OV5+)-V- horizontal ellipsis =O). While the vanadyl entity massively lowers the voltage of the V3+/V4+ and V4+/V5+ couples, it considerably improves the reversibility of these redox reactions. Therefore, anionic substitutions, mainly O2- by F-, have been identified as a strategy allowing for combining the beneficial effect of the vanadyl distortion on the reversibility with the high voltage of vanadium redox couples in fluorine rich environments.


Boivin, Edouard;  Chotard, Jean-Noel;  Masquelier, Christian;  Croguennec, Laurence

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