Organic-phase synthesis of Li₃V₂(PO₄)₃@Carbon nanocrystals and their lithium storage properties

Decreasing particle size is an efficient strategy for improving the lithium storage properties of Li₃V₂(PO₄)₃ (LVP) due to a shorter transport distances of lithium ion and electrons. However, designing and synthesizing LVP nanocrystals (NCs) with sizes smaller than 30 nm remains a challenge. In this work, we developed a facile approach for the fabrication of the monodisperse LVP NCs through a robust high-temperature organic-phase method. The thermodynamics of the synthesis and the possible reaction mechanism were investigated. The results indicate that the organic-phase environment (at 320 °C) may not thermodynamically allow the crystallization of LVP. Nevertheless, oleic acid (OA) and oleylamine (OAm) are essential as capping agents to hinder the agglomeration and growth of the particles. Based on the thermodynamic need, calcination is essential to prepare LVP. The surface electronic conductivity of the LVP NCs was enhanced through a subsequent carbon-coating treatment. The optimum combination of reduction and carbon coating is very favorable for the kinetics of electron transfer and lithium ion diffusion. Therefore, the fabricated LVP@C NCs exhibit superior lithium storage properties with excellent rate capability (84 mA h g^-1 at a rate of 20C) and perfect cyclic stability (96.2% capacity retention after 200 cycles at 5C), demonstrating their potential application in high-performance lithium-ion batteries.