Brillouin scattering investigation of solvation dynamics in succinonitrile-lithium salt plastic crystalline electrolytes

Abstract

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans–gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO₄ samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO₄ (∼0.3–1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (“compactness”). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as ν_f) as the temperature decreases. Anomalous temperature dependent behavior of ν_f with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes.