Insights into the Transport and Thermodynamic Properties of a Bis(fluorosulfonyl)imide-Based Ionic Liquid Electrolyte for Battery Applications

[Image: see text] Ionic liquid electrolytes (ILEs) have become popular in various advanced Li-ion battery chemistries because of their high electrochemical and thermal stability and low volatility. However, because of their relatively high viscosity and poor Li(+) diffusion, it is thought large concentration gradients form, reducing their rate capability. Herein, we utilize operando Raman microspectroscopy to visualize ILE concentration gradients for the first time. Specifically, using lithium bis(fluorosulfonyl)imide (LiFSI) in N-propyl-N-methylpyrrolidinium FSI, its “apparent” diffusion coefficient, lithium transference number, thermodynamic factor, ionic conductivity, and resistance of charge transfer against lithium metal were isolated. Furthermore, the analysis of these concentration gradients led to insights into the bulk structure of ILEs, which we propose are composed of large, ordered aggregates.