Lithium ion dynamics in Li2S+GeS2+GeO2 glasses studied using Li-7 NMR field-cycling relaxometry and line-shape analysis

Abstract

We use Li-7 NMR to study the ionic jump motion in ternary 0.5Li(2)S + 0.5[(1-x)GeS2+xGeO(2)] glassy lithium ion conductors. Exploring the "mixed glass former effect" in this system led to the assumption of a homogeneous and random variation of diffusion barriers in this system. We exploit that combining traditional line-shape analysis with novel field-cycling relaxometry, it is possible to measure the spectral density of the ionic jump motion in broad frequency and temperature ranges and, thus, to determine the distribution of activation energies. Two models are employed to parameterize the Li-7 NMR data, namely, the multi-exponential autocorrelation function model and the power-law waiting times model. Careful evaluation of both of these models indicates a broadly inhomogeneous energy landscape for both the single (x=0.0) and the mixed (x=0.1) network former glasses. The multi-exponential autocorrelation function model can be well described by a Gaussian distribution of activation barriers. Applicability of the methods used and their sensitivity to microscopic details of ionic motion are discussed. (C) 2015 Elsevier Inc. All rights reserved