Structural and dynamical properties of concentrated alkali- and alkaline-earth metal chloride aqueous solutions

Abstract

Concentrated ionic aqueous electrolytes possess a diverse array of applications across various fields, particularly in the field of energy storage. Despite extensive examination, the intricate relationships and numerous physical mechanisms underpinning diverse phenomena remain incompletely understood. Molecular dynamics simulations are employed to probe the attributes of aqueous solutions containing LiCl, NaCl, KCl, MgCl2, and CaCl2, spanning various solute fractions. The primary emphasis of the simulations is on unraveling the intricate interplay between these attributes and the underlying physical mechanisms. The configurations of cation-Cl− and Cl−–Cl− pairs within these solutions are disclosed. As the solute fraction increases, consistent trends manifest regardless of solute type: (i) the number of hydrogen bonds formed by the hydration water surrounding ions decreases, primarily attributed to the growing presence of counter ions in proximity to the hydration water; (ii) the hydration number of ions exhibits varying trends influenced by multiple factor; and (iii) the diffusion of ions slows down, attributed to the enhanced confinement and rebound of cations and Cl− ions from the surrounding atoms, concurrently coupled with the changes in ion vibration modes. In our analysis, we have, for the first time, clarified the reasons behind the slowing down of the diffusion of the ions with increasing solute fraction. Our research contributes to a better understanding and manipulation of the attributes of ionic aqueous solutions and may help designing high-performance electrolytes.