Structure, hydrogen bond dynamics and phase transition in a prototypical ionic liquid electrolyte

TL;DR

This study investigates the phase transition, hydrogen bond dynamics, and molecular mobility in the ionic liquid [TEA][NTf2], revealing a multistage melting process and how hydrogen bond strength influences physical properties.

Contribution

It provides detailed NMR analysis of the melting behavior and hydrogen bond dynamics in [TEA][NTf2], comparing it with related ionic liquids to elucidate the role of hydrogen bonds.

Findings

Dynamically heterogeneous phase between 223-277 K during melting

Multistage melting process with two enthalpy changes

Stronger hydrogen bonds result in higher activation barriers and lower libration amplitudes

Abstract

Ionic liquids (ILs) gain much interest as possible electrolytes in the next generation of mixed-solid Li-ion batteries. However, such properties of ionic liquids as melting transition, diffusion, strength and structure of hydrogen bond network remain poorly investigated. Here 2H NMR study of a prototypical ionic liquid [TEA][NTf2] has been performed. We show that the dynamical melting occurs through a dynamically heterogeneous phase stable between 223-277 K and the transition process is characterized by two standard molar enthalpy changes indicating to the multistage nature of the melting. The spin relaxation analysis allowed determining geometry, rates and energetics of IL mobility in both solid and liquid state. We compare these properties with previously reported data on [TEA][OTf] and [TEA][OMs] ILs that share cation but have anions of varying strength. Our results prove that the stronger hydrogen bonds between cation and anion lead to the lower enthalpy change between solid and liquid state, higher activation barrier of tumbling motion and lower amplitude of libration motion.