Dual‐Anionic Coordination Manipulation Induces Phosphorus and Boron‐Rich Gradient Interphase Towards Stable and Safe Sodium Metal Batteries.

High‐voltage sodium metal batteries (SMBs) present a viable pathway towards high‐energy‐density sodium‐based batteries due to the competitive cost advantage and abundant supply of sodium resources. However, they still suffer from severe capacity decay induced by the notorious decomposition of the electrolyte under high voltage and unstable cathode/electrolyte interphase (CEI). In addition, the high reactivity of Na metal and flammable electrolytes push SMBs to their safety limits. Herein, a special dual‐anion aggregated Na+ solvation structure is designed in a nonflammable trimethyl phosphate‐based localized high‐concentration electrolyte, and a gradient CEI enriched with phosphorus and boron compounds is formed on the cathode. This thin and stable interphase effectively suppresses the parasitic reaction, improves the interfacial stability of the cathode, and facilitates Na+ transport through the interface by the synergistic effect of multi‐components, thus optimizing the cycling stability and safety of SMBs. The Na0.95Ni0.4Fe0.15Mn0.3Ti0.15O2//Na batteries employing such electrolyte provide a discharge capacity of 167.5 mAh g−1 and high retention in the capacity of 85.2 % after 800 cycles at 1 C. This approach offers a general strategy for the design of flame‐retardant high‐voltage electrolytes and the practical application of SMBs. [ABSTRACT FROM AUTHOR]