The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.
Revised: August 28, 2020 |
Published: November 14, 2016
Citation
Han K., N. Rajput, M. Vijayakumar, X. Wei, W. Wang, J.Z. Hu, and K.A. Persson, et al. 2016.Preferential Solvation of an Asymmetric Redox Molecule.Journal of Physical Chemistry C 120, no. 49:27834-27839.PNNL-SA-113547.doi:10.1021/acs.jpcc.6b09114