High-capacity sodium (Na) anodes suffer from dendrite growth due to the high reactivity, which can be overcome through inducing a stable NaF-rich solid electrolyte interphase (SEI). Herein, we propose an additive strategy for realizing the anion-enriched structure of Na solvation to obtain a NaF-rich SEI. The electron-withdrawing acetyl group in 4-acetylpyridine (4-APD) increases the coordination number of PF in the Na solvation sheath to facilitate PF to decompose into NaF. Thus, the NaF-rich SEI with high mechanical stability and interfacial energy is formed to repress the growth of Na dendrites. With the 4-APD-contained electrolyte, the symmetric Na||Na cells show excellent cycling performance over 360 h at 1.0 mA cm . Meanwhile, excellent stability is also achieved for Na||Na V (PO ) O F full cells with high Coulombic efficiency (97 %) and capacity retention (91 %) after 200 cycles.
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