A robust, highly reversible, mixed conducting sodium metal anode

Sodium metal anode holds great promise in pursuing high-energy and sustainable rechargeable batteries, but severely suffers from fatal dendrite growth accompanied with huge volume change. Herein, a robust mixed conducting sodium metal anode is designed through incorporating NaSICON-type solid Na-ion conductor into bulk Na. A fast and continuous pathway for simultaneous transportation of electrons and Na⁺ is established throughout the composite anode. The intimate contact between Na-ion conducting phase and Na metallic phase constructs abundant two-phase boundaries for fast redox reactions. Further, the compact configuration of the composite anode substantially protects Na metal from being corroded by liquid organic electrolyte for the minimization of side reactions. Benefiting from the unique configuration, the composite anode shows highly reversible and durable Na plating/stripping behavior. The symmetric cells exhibit ultralong lifespan for over 700 h at 1 mA cm^-2 with a high capacity of 5 mAh cm^-2 and outstanding rate capability up to 8 mA cm^-2 in the carbonate electrolyte. Full cells with Na₃V₂(PO₄)₃/C cathode demonstrate impressive cycling stability (capacity decay of 0.012% per cycle) and low charge/discharge polarization as well. This work provides new insights into rational design and development of robust sodium metal anode through an architecture engineering strategy for advanced rechargeable sodium batteries.