Two-dimensional diffusion in Li0.7NbS2 as directly probed by frequency-dependent 7Li NMR.

Li ion diffusion in layer-structured Li0.7NbS2 has been complementary investigated by nuclear magnetic resonance (NMR) spectroscopy from an atomic scale point of view. In the present case, (7)Li NMR spin-lattice relaxation (SLR) rates R1ρ probed in the rotating frame of reference proved very informative in characterizing the Li self-diffusion process in the van der Waals gap between the NbS2 layers. While temperature-variable SLRρ measurements were used to determine dynamic parameters such as jump rates (τ(-1)) and the activation energy (Ea), frequency-dependent measurements were used to specify the dimensionality of the diffusion process. In particular, the effect of annealing, i.e., the distribution of Li ions between the layers, on overall Li dynamics has been studied. When plotted in an Arrhenius diagram, the R1ρ rates of an annealed sample, which were recorded at a locking frequency of 20 kHz, pass through a diffusion-induced relaxation peak whose maximum shows up at 320 K. Employing an appropriate diffusion model and appropriately accounting for a non-diffusive background relaxation, a Li jump rate τ(-1)(300 K) ≈ 1.3 × 10(5) s(-1) and an activation energy Ea of 0.43(2) eV can be deduced. Most importantly, in the high-T limit of the diffusion-induced rate peak, i.e., when ω1τ << 1 holds, the rates follow a logarithmic frequency dependence. This points to a diffusion process of low dimensionality and is in good agreement with predictions of relaxation models developed for 2D diffusion.