Probing magnetic order in LiMPO4, M = Ni, Co, Fe and lithium diffusion in LixFePO4

Muon spin relaxation measurements are reported on three members of the LixMPO4 series. The magnetic properties of stoichiometric samples with M = Ni, Co, Fe, were investigated at low-temperature. In LiNiPO4 we observe different forms of the muon decay asymmetry in the commensurate and incommensurate antiferromagnetic phases, accompanied by a change in the temperature dependence of the muon oscillation frequency. In LiCoPO4 the form of the muon decay asymmetry indicates that the correlation between layers decreases as the Neel temperature is approached from below. LiFePO4 shows more conventional behaviour, typical for an antiferromagnet. Measurements on LixFePO4 with x = 0.8, 0.9, and 1 show evidence for lithium diffusion below ~250 K and muon diffusion dominating the form of the relaxation at higher temperature. The thermally activated form of the observed hopping rate suggests an activation barrier for lithium diffusion of ~ 100 meV and a diffusion constant of D_Li ~ 10^-10 - 10^-9 cm2/s at room temperature.