Lithium diffusion in LiMnPO4 detected with μ±SR

Positive- and negative-muon spin rotation and relaxation (mu(+/-) SR) was first used to investigate fluctuations of nuclear magnetic fields in an olivine-type battery material, LiMnPO4, in order to clarify the diffusive species, namely, to distinguish between a mu(+) hopping among interstitial sites and Li+ ions diffusing in the LiMnPO4 lattice. Muon diffusion can only occur in mu+SR, because the implanted mu(-) forms a stable muonic atom at the lattice site, and therefore any change in linewidth measured with mu-SR must be due to Li+ diffusion. Since the two measurements exhibit a similar increase in the field fluctuation rate with temperature above 100 K, it is confirmed that Li+ ions are in fact diffusing. The diffusion coefficient of Li+ at 300 K and its activation energy were estimated to be 1.4(3) x 10(-10) cm(2)/s and 0.19(3) eV, respectively. Such combined mu(SR)-S-+/- measurements are thus shown to be a suitable tool for detecting ion diffusion in solid-state energy materials.