Structural, electrochemical, electronic, and magnetic properties of monoclinic LixV2(PO4)3 for x = 3, 2, 1 using first-principles calculations.

Monoclinic lithium vanadium phosphate Li3V2(PO4)3 is a very promising cathode candidate for applications in Li-ion batteries, with a high operational voltage (~ 4 V vs. Li+/Li) and a high theoretical capacity of 197 mAh/g. However, the underlying electrochemical mechanism of monoclinic Li3V2(PO4)3 is not yet fully understood, due to its complexity. To gain more knowledge about the electrochemical performance of the monoclinic Li3V2(PO4)3, we perform density functional calculations of structural, electrochemical, electronic, and magnetic properties of LixV2(PO4)3 for x = 3, 2, 1, based on the full-potential linearized augmented plane wave (FP-LAPW) method. The generalized gradient approximation corrected with the present work self-consistently calculated Hubbard parameter U (GGA+U method) shows that it can successfully reproduce the experimental average lithium intercalation voltage for the redox couple V4+/V3+ within 7% error, and within 2% error for the transition x: 3 ➔ 2. The present work method is fully ab initio and without any arbitrary parameters. In the literature, the existence of charge ordering in Li2V2(PO4)3 is subject to discrepancy. By analyzing the present calculated structural, magnetic, and electronic properties of Li2V2(PO4)3, the existence of charge ordering had been confirmed. The present work method sets the path for accurately predicting the redox potential of future lithium and sodium phosphate compounds for the next-generation batteries technology. [ABSTRACT FROM AUTHOR]