Solvation structure-property relationships in high-concentration sodium electrolytes: Insights from molecular simulations

Sodium-ion batteries (SIBs) are promising cost-effective and sustainable alternatives to lithium-ion batteries (LIBs) for large-scale energy storage. However, their development is limited by slow ion transport due to the larger ionic radius of Na + and challenges in forming stable solid electrolyte interphases (SEIs). Moreover, fundamental differences in ionic size, chemical reactivity, and electrochemical behavior between Na + and Li + hinder the direct transfer of design principles from LIBs to SIBs. To address these issues, electrolyte engineering, particularly with high-concentration electrolytes, has shown potential to enhance interfacial stability and suppress dendrite formation. In this study, we applied a combination of density functional theory (DFT), ab initio molecular dynamics (AIMD), and classical molecular dynamics (CMD) simulations to investigate solvation structure-property relationships in sodium bis(fluorosulfonyl)imide dimethoxyethane (NaFSI/DME) electrolytes. Our results reveal that, at low concentrations (1–2 M), Na + primarily forms solvent-separated and contact ion pairs, and ion transport is dominated by vehicular motion involving co-diffusion with FSI − . Free DME molecules are readily reduced, forming reactive intermediates such as sodium methoxide (NaOCH 3 ), which destabilize the SEI. At high concentrations (4–5 M), Na + is preferentially coordinated by FSI − , forming extended ionic aggregates. The transport mechanism shifts to structural diffusion, where Na + migrates by hopping between FSI − sites, resulting in increased correlated transference numbers. Moreover, the reduction of Na-FSI-DME clusters favors the formation of stable SEI components such as NaF and Na 2 O. These findings elucidate how solvation environments and ion transport mechanisms evolve with concentration and highlight the critical role of high-concentration electrolytes in stabilizing interfacial chemistry. This work offers molecular-level insights to guide the design of Na electrolytes with enhanced ion dynamics and robust SEI formation. • MD reveals solvation evolution in NaFSI/DME electrolytes across 1–5 M. • Na + transport transitions from vehicular to structural motion. • Ion clusters raise correlated transference number despite reduced conductivity. • Electron-injection AIMD shows 1 M forms NaOCH 3 -rich SEI, while 5 M yields NaF/Na 2 O.