Formation of NaF‐Rich Solid Electrolyte Interphase on Na Anode through Additive‐Induced Anion‐Enriched Structure of Na+Solvation

Abstract 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 6 − in the Na + solvation sheath to facilitate PF 6 − 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 −2 . Meanwhile, excellent stability is also achieved for Na||Na 3 V 2 (PO 4 ) 2 O 2 F full cells with high Coulombic efficiency (97 %) and capacity retention (91 %) after 200 cycles.