Size-Dependent Lithium Miscibility Gap in Nanoscale Li[sub 1−x]FePO[sub 4]

Olivine compounds have emerged as important and enabling positive electrode materials for high-power, safe, long-life lithium rechargeable batteries. In this work, the miscibility gap in undoped is shown to contract systematically with decreasing particle size in the nanoscale regime and with increasing temperature at a constant particle size. These effects suggest that the miscibility gap completely disappears below a critical size. In the size-dependent regime, the kinetic response of nanoscale olivines should deviate from the simple size-scaling implicit in Fickian diffusion.