We present an ultraconcentrated electrolyte composed of 5 M sodium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane for Na metal anodes coupled with high-voltage cathodes. Using this electrolyte, a very high Coulombic efficiency of 99.3% at the 120th cycle for Na plating/stripping is obtained in Na/stainless steel (SS) cells with highly reduced corrosivity toward Na metal and high oxidation durability (over 4.9 V versus Na/Na) without corrosion of the aluminum cathode current collector. Importantly, the use of this ultraconcentrated electrolyte results in substantially improved rate capability in Na/SS cells and excellent cycling performance in Na/Na symmetric cells without the increase of polarization. Moreover, this ultraconcentrated electrolyte exhibits good compatibility with high-voltage NaFe(PO)(PO) and Na(FeMn)O cathodes charged to high voltages (>4.2 V versus Na/Na), resulting in outstanding cycling stability (high reversible capacity of 109 mAh g over 300 cycles for the Na/NaFe(PO)(PO) cell) compared with the conventional dilute electrolyte, 1 M NaPF in ethylene carbonate/propylene carbonate (5/5, v/v).
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