Tuning Solid Electrolyte Interphase Formation before Plating Onset in Anode-Free Sodium Batteries

Sodium (Na) batteries are of growing interest due to the higher earth abundance of sodium than lithium, as well as their promising theoretical energy density when metallic Na anodes are used. However, Na plating and stripping are heavily influenced by the physicochemical properties of the solid electrolyte interphase (SEI), which is directly influenced by the solvent and salt used for the electrolyte. While most studies focus on the SEI that forms on the surface of Na metal after plating, we expand this analysis by identifying a nanoscale “pre-plating” SEI that forms on the current collector (CC) prior to the onset of Na plating. Here, we systematically investigate an array of Na salt and glyme solvents in the electrolyte and determine the associated impacts on pre-plating SEI formation on aluminum CCs. By combining analytical electrochemistry approaches with a multimodal suite of spectroscopy techniques (X-ray, infrared, and Raman), supported by density functional theory calculations, we reveal a direct correlation between the Na⁺ coordination environment and pre-plating SEI composition. We find that longer-chain glymes produce larger proportions of organic alkoxide products in the interphase, consistent with increased Na⁺–glyme interactions, while the fraction of salt-derived inorganic products (e.g., NaF) correlates with Na⁺–anion coordination. These insights highlight the critical influence of electrolyte composition─particularly solvent identity and Na⁺ coordination─on the initial SEI formation in anode-free Na batteries.