Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents

Nonaqueous redox-flow batteries (NARFBs) that use economical alkali metals and the corresponding metal polysulfides are highly attractive for grid-scale energy storage. Although sodium–sulfur systems have been recognized as promising candidates and have been the focus of many studies due to their high earth abundance and energy density, an understanding of the role of the solvation chemistry of commonly used glyme solvents is missing. Herein, we report a systematic investigation into the solvation effects of glyme-based Na-S electrolytes through comprehensive physiochemical experiments and Density Functional Theory (DFT) simulations. Our findings revealed, on one hand, that an optimal coordination strength between glymes and Na+ could maintain a relatively smooth Na+ diffusion. On the other hand, glyme solvents with extended chain lengths shift the reduction potential of S82– negatively to elevate the formation barrier of undesirable short-chain polysulfides (Sn2–, n ≤ 4) that have high membrane permeability. This solvation phenomenon not only mitigates capacity fading but also extends the operational longevity of the Na-S NARFBs. The results underscore the critical roles of balanced solvent–cation interactions and controlled redox potentials in improving the stability and efficiency of Na-S NARFB systems, marking a significant advancement in the development of sustainable energy storage solutions.