Superior charge-transfer kinetics of NASICON-type Li3V2(PO4)3 cathodes by multivalent Al3+ and Cl− substitutions

The kinetic properties of Li insertion in NASICON-type Li3V2(PO4)3 cathodes were enhanced substantially by Al3+ and Cl− multivalent substitutions of various concentrations. Pristine and carbon coated, Al-doped Li3V2(PO4)3 were also prepared by a conventional solid-state approach under optimized conditions. Samples phase purity was investigated through X-ray diffractometry. Li insertion was studied in half-cells at 3-4.8 V vs. Li for the removal of 3 mol of Li. Carbon-coated Li3V1.98Al0.02(PO4)2.99Cl0.01 showed the highest reversible insertion of 2.71 mol of Li (178 mAh g−1) at a current density of 0.2 mA cm−2. It showed a capacity retention of over 80% after 100 cycles. Cl− substitution led to improved performance under harsh conditions of 15 C rate and high temperature (50 °C). The enhancement of Li ion kinetics was demonstrated through cyclic voltammetry in a two-electrode configuration and electrochemical impedance spectroscopy confirmed the enhanced conductivity.

Graphical abstractSuperior kinetic properties are noted for the multivalent Al3+ and Cl− substituted NASICON type Li3V2(PO4)3 cathodes, which enables extraordinary cycling performance especially at high current rates.Figure optionsDownload full-size imageDownload as PowerPoint slide