“…Due to the mounting demands for renewable energy and the development of grid-scale energy, aqueous Na-ion batteries (ANIBs), which possess the merits of inherent safety, abundant reserves, and high ionic conductivity, have been regarded as promising alternatives in the era of organic batteries. − However, with water as the solvent, conventional dilute aqueous electrolytes restrict the multiscenario and all-climate applications of ANIBs, which have been naturally imputed to the high activity of water molecules. − Along this line, varied research has focused on the modification of aqueous electrolytes and has developed numerous approaches to widen the electrochemical window and lower the freezing points, such as the introduction of the “water-in-salt” concept − and organic additives. − Besides, the artificial solid electrolyte interphase (SEI) layer could kinetically prevent water molecules from penetrating the electrode materials, thus inhibiting water electrolysis. , Nevertheless, the effects of an interface toward the low-temperature performance of ANIBs remain elusive, which is worth exploring in this field. In organic batteries, the high interfacial resistance linking to desolvation energy and SEI begets battery failure at low temperatures, where the verified failure mechanisms have been employed to guide the optimization of solvation structures, thus addressing the poor low-temperature performance. , Compared with organic systems, ANIBs mostly derive a thin and unstable SEI, yet the distributions of charge carriers and water molecules in the inner Helmholtz plane (IHP) still need much attention at low temperatures.…”