NaF-Rich Multifunctional Layers toward Stable All-Solid-State Sodium Batteries

NASICON oxide solid electrolytes are considered promising candidates for all-solid-state sodium batteries due to their extremely high ionic conductivity and favorable electrochemical stability. However, the practical application of NASICON electrolytes is greatly impeded by poor electrolyte-electrode interfacial contact and continuous sodium dendrite propagation. Herein, a NaF-rich multifunctional interface layer on the surface of a Na anode (Na@NaF-rich), containing NaF, amorphous carbon, and an unreacted C-F bond species, is developed in situ by the reaction between Na and commercial poly(tetrafluoroethylene). This NaF-rich interface layer is proven to reduce the diffusion barriers at the Na/NASICON electrolyte interface and homogenize Na deposition as well as suppress Na dendrite growth, thus achieving a high critical current density of 4 mA cm^-2. The resultant Na₃V₂(PO₄)₃@C/Na@NaF-rich all-solid-state cell showed a high initial specific capacity of 117.6 mAh g^-1 at 0.1 C with a Coulombic efficiency of 94.8%. Even at 0.5 and 1 C, it still exhibited high capacity retentions of 83.3% and 80.4%, respectively, after 750 cycles.