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Aqueous sodium-ion batteries (ASIBs) offer important advantages in terms of safety, ionic conductivity, environmental friendliness, and cost-effectiveness. However, their industrial development has been hindered by a narrow electrochemical stability window (ESW) and suboptimal energy density. In this work, a cost-effective high-entropy electrolyte formulation was developed, consisting of 6 M sodium acetate (NaAc) and 2 M zinc acetate [Zn(Ac)2]. The introduced Zn(Ac)2 not only effectively disrupted the hydrogen bonds between water molecules but also dramatically reduced the bound water in the first solvation of Na. It demonstrated that such an entropy-driving structure could efficiently expand the ESW up to 2.68 V and substantially lower the freezing point of the electrolyte to −79 ℃. As a result, the optimized electrolyte enabled the full cell to achieve a high energy density of 190 Wh/kg and maintained 60.3% of its capacity at −40 ℃ compared to room temperature. This work provides scientific insights for designing high-entropy electrolytes for sodium storage over a wide temperature range.
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