Ion and polymer dynamics in polymer electrolytes PPO-LiClO4: insights from NMR line-shape analysis

TL;DR

This study uses NMR line-shape analysis to explore ion and polymer dynamics in PPO-LiClO4 electrolytes, revealing coupling between ion and polymer motions, dynamical heterogeneities, and continuous distributions of segmental relaxation times.

Contribution

It provides detailed insights into the coupling and heterogeneity of ion-polymer dynamics in PPO-LiClO4 electrolytes through advanced NMR analysis, highlighting the impact of salt concentration.

Findings

Polymer segmental motion slows down with increased salt content.

Dynamical heterogeneities are prominent at intermediate salt levels.

Polymer relaxation involves small-angle rotational jumps.

Abstract

We investigate ion and polymer dynamics in polymer electrolytes PPO-LiClO4 performing 2H and 7Li NMR line-shape analysis. Comparison of temperature dependent 7Li and 2H NMR spectra gives evidence for a coupling of ion and polymer dynamics. 2H NMR spectra for various salt concentrations reveal a strong slow down of the polymer segmental motion when the salt content is increased. The 2H NMR line shape further indicates that the segmental motion is governed by dynamical heterogeneities. While the width of the distribution of correlation times G(log tau) is moderate for low and high salt content, an extremely broad distribution exists for an intermediate salt concentration 15:1 PPO-LiClO4. For the latter composition, a weighed superposition of two spectral components, reflecting the fast and the slow polymer segments of the distribution, describes the 2H NMR line shape over a broad temperature range. Analysis of the temperature dependent relative intensity of both spectral components indicates the existence of a continuous rather than a discontinuous distribution G(log tau). Such continuous distribution is consistent with gradual fluctuation of the local salt concentration and, hence, of the local environments of the polymer segments, whereas it is at variance with the existence of large salt-depleted and salt-rich domains featuring fast and slow polymer dynamics, respectively. Finally, for all studied mixtures PPO-LiClO4, the 2H NMR line shape strongly depends on the echo delay in the applied echo-pulse sequence, indicating that the structural relaxation of the polymer segments involves successive rotational jumps about small angles gamma<20 degree.