Reversible Ionic Aggregation Kinetics in Concentrated Electrolytes

Here we develop a formalism for reversible ionic aggregation kinetics in an example concentrated electrolyte, building on previous equilibrium work of McEldrew and co-workers, and thermoreversible polymers and patchy particle systems. This is achieved through solving a macroscopic rate equation of open/occupied association sites, shown to be a solution of the reversible Smoluchowski aggregation equation, which predicts how ionic associations in electrolytes change subject to a step-change in conditions. We test the derived equations against atomistic molecular dynamics simulations of a salt-in-ionic liquid, where good qualitative agreement is obtained, but quantitative differences are found. This highlights the multiple time scales that exist in concentrated electrolytes, with a fast timescale preceding a longer timescale. We hope this formalism opens new avenues in understanding the dynamics and non-equilibrium behaviour in electrolytes. For example, the formalism can be developed further to investigate the non-Newtonian behaviour of concentrated electrolytes, double layer charging, and the slow dynamics of these electrolytes in confinement.

Zachary A. H. Goodwin · 2026