Electrochemical Performance of Nanosized Disordered LiVOPO(4)

[Image: see text] ε-LiVOPO(4) is a promising multielectron cathode material for Li-ion batteries that can accommodate two electrons per vanadium, leading to higher energy densities. However, poor electronic conductivity and low lithium ion diffusivity currently result in low rate capability and poor cycle life. To enhance the electrochemical performance of ε-LiVOPO(4), in this work, we optimized its solid-state synthesis route using in situ synchrotron X-ray diffraction and applied a combination of high-energy ball-milling with electronically and ionically conductive coatings aiming to improve bulk and surface Li diffusion. We show that high-energy ball-milling, while reducing the particle size also introduces structural disorder, as evidenced by (7)Li and (31)P NMR and X-ray absorption spectroscopy. We also show that a combination of electronically and ionically conductive coatings helps to utilize close to theoretical capacity for ε-LiVOPO(4) at C/50 (1 C = 153 mA h g(–1)) and to enhance rate performance and capacity retention. The optimized ε-LiVOPO(4)/Li(3)VO(4)/acetylene black composite yields the high cycling capacity of 250 mA h g(–1) at C/5 for over 70 cycles.