Cyclic ethers are promising solvents for low-temperature electrolytes, but they still suffer from intrinsic poor antioxidant abilities. Until now, ether-based electrolytes have been rarely reported for high-voltage sodium-ion batteries (SIBs) operated under a low-temperature range. Herein, a novel ether-based electrolyte consisting of tetrahydrofuran as the main solvent is proposed and it could be utilized for a high-voltage Na2/3Mn2/3Ni1/3O2 (MN) cathode in a wide-temperature range from −40 to 25 °C. Meanwhile, a thin and robust inorganic component-rich cathode electrolyte interface layer is elaborately introduced on the MN cathode by this tailored electrolyte, resulting in excellent cycle life of MN cathode. Specifically, a capacity retention of 97.2% after 140 cycles could be delivered by MN at 0.3 C at room temperature (RT). Especially at an ultra-low temperature of −40 °C, the initial discharge capacity of MN could still approach 89.3% of that at RT, and the capacity retention is 94.1% at 0.2 C after 100 cycles. This work provides a new insight into the rational design of ether-based electrolytes for high-voltage and stable SIBs operated in a wide-temperature range.

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