Reversible ionic aggregation kinetics in concentrated electrolytes

Journal article

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 tested 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.

Authors: Goodwin, ZAH

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Royal Society of Chemistry
• Journal: Chemical Science
• Publication date: 2026-05-12
• Acceptance date: 2026-05-09
• DOI: 10.1039/d6sc01986b
• EISSN: 2041-6539
• ISSN: 2041-6520
• Language: English
• Keywords: Kinetics; Electrolyte; Ionic bonding; Formalism (music); Polymer; Work (physics); Polymer electrolytes