Nonstoichiometry Induced Amorphous Grain Boundary of Na₅SmSi₄O₁₂ Solid-State Electrolyte for Long-Life Dendrite-Free...

Oxide ceramics are considered promising candidates as solid electrolytes (SEs) for sodium metal batteries. However, the high sintering temperature induced boundaries and pores between angular grains lead to high grain boundary resistance and pathways for dendrite growth. Herein, we report a grain boundary modification strategy, which in situ generates an amorphous matrix among Na₅SmSi₄O₁₂ oxide grains via tuning the chemical composition. The mechanical properties as well as electron mitigating capability of modified SE have been significantly enhanced. As a result, the SE achieves a room-temperature total ionic conductivity of 5.61 mS cm^-1, the highest value for sodium-based oxide SEs. The Na|SE|Na symmetric cell achieves a high critical current density of 2.5 mA cm^-2 and excellent cycle life over more than 2800 h at 0.15 mA cm^-2 without dendrite formation. The full cell with Na₃V₂(PO₄)₃ as the cathode demonstrates impressive cycling performance, maintaining stability over 3000 cycles at 5C without observable loss of capacity.