Correlating Ionic Conductivity to Structure and Dynamics of Li-Ion Battery Electrolyte Systems: Raman Spectroscopy, Dielectric Relaxation Measurements, and Streak Camera Solvation Data Analysis.

A correlation between ionic conductivity and electrolyte solution structure and dynamics was explored by performing electrolyte concentration- and temperature-dependent measurements of conductivity, viscosity, and dielectric relaxation (DR) in solutions of lithium bis(trifluoromethane)sulfonimide (LiTFSI) in triethylene glycol dimethyl ether (also known as triglyme, G3). In addition, an electrolyte concentration-dependent Raman spectroscopic study and ultrafast dynamic fluorescence Stokes shift measurements of solvation of a dissolved solute by employing a streak camera detection technique were carried out. Measured conductivities (σ) and the average DR times (⟨τ_DR⟩) were found to be partially decoupled from the solution viscosities (η) and obeyed the relation, σ or ⟨τ_DR⟩^-1 ∝(η/T)^-p, with p = 0.6-0.75 for σ and p = 0.2-0.45 for ⟨τ_DR⟩^-1. Raman data indicated the formation of ion pairs and ionic aggregates in these solutions, while the measured glass transition temperature increased with LiTFSI concentration. Conductivities (σ) showed a nonlinear concentration dependence but increased linearly with the solution static dielectric constants (ε_s). The latter may be explained by considering the temperature effects on complex electrolyte species and the subsequent solution dielectric behavior. Interestingly, an inverse power-law dependence of σ on the measured DR or solvation time scales, σ ∝ (τ_x)^-m, with m = 1.2-1.9, was observed. This dependence may be explained by considering that the same environmental friction regulates both the ion diffusion and the medium polarization relaxation. The control of a slow process (ion translation) by relatively faster medium dynamics (dipolar rotation), although quite fascinating for the present system, warrants further experimental scrutiny for other electrolyte systems relevant to battery applications.