Materials with the olivine LixMPO4 structure form an important class of rechargeable battery cathodes. Using first-principles methods, activation barriers to Li ion motion were calculated and an estimate for Li diffusion constants, in the absence of electrical conductivity constraints, was made. Materials with M = Mn, Fe, Co, Ni were considered. Li diffused through 1-dimensional channels with high energy barriers to cross between the channels. Without electrical conductivity limitations the intrinsic Li diffusivity was high.

Li Conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) Olivine Materials. D.Morgan, A.Van der Ven, G.Ceder: Electrochemical and Solid-State Letters, 2004, 7[2], A30-2