Nuclear Magnetic Resonance Dynamics of LiTFSI–Pyrazole Eutectic Solvents

Deep Eutectic Solvents (DESs) have emerged as promising candidates to replace conventional organic solvents in various technological applications due to their low vapor pressure, non-flammability, and ease of preparation at low costs. In particular, Type IV DESs, which are composed of metal salts and hydrogen bond donors, are possible replacements for lithium-ion battery electrolytes. In this study, we investigate the molecular dynamics of solvents of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and pyrazole (PYR) at varying LiTFSI:PYR molar ratios (1:2, 1:3, 1:4, 1:5) using Nuclear Magnetic Resonance Dispersion (NMRD) and Pulsed Field Gradient (PFG) Nuclear Magnetic Resonance (NMR). PFG NMR reveals composition-dependent diffusion trends, while NMRD provides molecular-level insights into the longitudinal relaxation rate (R1 = 1/T1). Notably, the LiTFSI:PYR (1:2) sample shows distinct behavior across both techniques, exhibiting enhanced relaxation rates and lower self-diffusion for 1H compared to the other nuclei (19F and 7Li), suggestive of stronger and more efficient Li+–pyrazole interactions, as confirmed by the modeling of the relaxation profiles. Our study advances understanding of ion dynamics in azole-based eutectic solvents, supporting their potential use in safer battery electrolytes.