Relation of short-range and long-range lithium ion dynamics in glass-ceramics: Insights from Li-7 NMR field-cycling and field-gradient studies
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Abstract
We use various Li-7 NMR methods to investigate lithium ion dynamics in 70Li(2)S-30P(2)S(5) glass and glass-ceramic obtained from this glass after heat treatment. We employ Li-7 spin-lattice relaxometry, including field-cycling measurements, and line-shape analysis to investigate short-range ion jumps as well as Li-7 field-gradient approaches to characterize long-range ion diffusion. The results show that ceramization substantially enhances the lithium ion mobility on all length scales. For the 70Li(2)S-30P(2)S(5) glass-ceramic, no evidence is found that bimodal dynamics result from different ion mobilities in glassy and crystalline regions of this sample. Rather, Li-7 field-cycling relaxometry shows that dynamic susceptibilities in broad frequency and temperature ranges can be described by thermally activated jumps governed by a Gaussian distribution of activation energies g( E-a) with temperature-independent mean value E-m = 0.43 eV and standard deviation sigma = 0.07 eV. Moreover, use of this distribution allows us to rationalize Li-7 line-shape results for the local ion jumps. In addition, this information about short-range ion dynamics further explains Li-7 field-gradient results for long-range ion diffusion. In particular, we quantitatively show that, consistent with our experimental results, the temperature dependence of the self-diffusion coefficient D is not described by the mean activation energy E-m of the local ion jumps, but by a significantly smaller apparent value whenever the distribution of correlation times G( log tau) of the jump motion derives from an invariant distribution of activation energies and, hence, continuously broadens upon cooling. This effect occurs because the harmonic mean, which determines the results of diffusivity or also conductivity studies, continuously separates from the peak position of G( log tau) when the width of this distribution increases.
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This article is published as Haaks, Michael, Steve W. Martin, and Michael Vogel. "Relation of short-range and long-range lithium ion dynamics in glass-ceramics: Insights from Li 7 NMR field-cycling and field-gradient studies." Physical Review B 96, no. 10 (2017): 104301. doi: 10.1103/PhysRevB.96.104301. Posted with permission.