Molecular dynamics (MD) simulations of acetonitrile (AN) mixtures with LiBF4, LiCF3SO3 and LiCF3CO2 provide extensive details about the molecular- and mesoscale-level solution interactions and thus explanations as to why these electrolytes have very different thermal phase behavior and electrochemical/physicochemical properties. The simulation results are in full accord with a previous experimental study of these (AN)n-LiX electrolytes. This computational study reveals how the structure of the anions strongly influences the ionic association tendency of the ions, the manner in which the aggregate solvates assemble in solution and the length of time in which the anions remain coordinated to the Li+ cations in the solvates which result in dramatic variations in the transport properties of the electrolytes.
Revised: October 30, 2015 |
Published: January 14, 2015
Citation
Borodin O., S.D. Han, J.S. Daubert, D.M. Seo, S. Yun, and W.A. Henderson. 2015.Electrolyte Solvation and Ionic Association. VI. Acetonitrile-Lithium Salt Mixtures: Highly Associated Salts Revisited.Journal of the Electrochemical Society 162, no. 4:A501-A510.PNNL-SA-106778.doi:10.1149/2.0891503jes