Journal
JOURNAL OF PHYSICS-CONDENSED MATTER
Volume 25, Issue 19, Pages -Publisher
IOP PUBLISHING LTD
DOI: 10.1088/0953-8984/25/19/195402
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Funding
- Deutsche Forschungsgemeinschaft (DFG) within the framework of the Research Unit [FOR 1277]
- Graz University of Technology (Austria) [WI3600/2-2, 4-2]
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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, Li-7 NMR spin-lattice relaxation (SLR) rates R-1 rho 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 SLR rho measurements were used to determine dynamic parameters such as jump rates (tau(-1)) and the activation energy (E-a), 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 R-1 rho 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 tau(-1) (300 K) approximate to 1.3 x 10(5) s(-1) and an activation energy E-a of 0.43(2) eV can be deduced. Most importantly, in the high-T limit of the diffusion-induced rate peak, i.e., when omega(1)tau << 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.
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