Effect of VO₄ ^3– Substitution on the Electrochemical Properties of a LiSn₂(PO₄)₃ Anode Material

Abstract

LiSn₂(PO₄)₃ anion was used to partially substitute for VO₄ ^3– in the Nasicon compound of LiSn₂(PO₄)₃ via a sol-gel method. XRD analysis revealed that the LiSn₂(PO₄)₃-substituted samples did not have a single LiSn₂(PO₄)₃ phase, and some secondary phases like SnO₂ and SnP2O7 appeared. Introduction of the LiSn₂(PO₄)₃ anion did not prevent the LiSn₂(PO₄)₃ compound from decomposing during the initial lithiation; however the LiSn₂(PO₄)₃ anion substitution remarkably enhanced the rate capability and cycling performance of the products because they reduced the charge transfer impedance, increased the lithium ion diffusion, and strengthened the role of the Li₃VO₄ matrix due to the precipitation of the Li₃VO₄ phase. Of the substituted samples, the sample with a nominal composition of LiSn₂(PO₄)_2.5(VO₄)_0.5 delivered a capacity of 449.2 mA·h/g at a rate of 0.25 C after 25 cycles and 373.8 mA·h/g at 2 C rate. Those values surpassed some previous reports on LiSn₂(PO₄)₃ and the LiSn₂(PO₄)₃/C composites. Accordingly, the partial substitution of phosphorus by vanadium in LiSn₂(PO₄)₃ is a feasible technique to remarkably improve its electrochemical properties.

Keywords

Sn-based material / Anode material / LiSn₂(PO₄)₃ / VO₄ ^3– substitution / Electrochemical property

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