Extremely slow cation exchange processes in Li4SiO4 probed directly by two-time 7Li stimulated-echo nuclear magnetic resonance spectroscopy

Lithium self-diffusion in the low-temperature modification of polycrystalline lithium ortho-silicate Li4SiO4 is investigated by 7Li two-time stimulated echo NMR spectroscopy. Extremely slow Li exchange processes were directly monitored between 300 and 433 K by recording spin-alignment echoes as a function of mixing time varying over six decades from 10-5 to 10 s. In the investigated temperature range the hopping correlation functions show biexponential behaviour. Whereas the first decay step reflects directly Li jumps between electrically different sites, the second one is simply induced by the decay of alignment order due to quadrupolar relaxation. The echo decay rates τ-1 (101 s-1≤τ-1≤104 s-1), which can be identified with Li jump rates, show Arrhenius behaviour with an activation energy of 0.53(1) eV. The directly measured jump rates are in good agreement with those obtained recently by one- and two-dimensional 6Li exchange MAS NMR reported in the literature