Increase ionic conductivity of a Zn2+/F− synergy Na3Zr2Si2PO12 solid electrolyte for sodium metal batteries

Na3Zr2Si2PO12 (NZSP) solid-state electrolyte is considered one of the most promising solid-state electrolyte because of their excellent electrochemical and thermal stability. Even though, the low conductivity of NZSP solid-state electrolytes hinders practical application. Therefore, an anions/cations co-assisting strategy is proposed by introducing the Zn2+ and F−. The influence of adding different amounts of Zn2+ and F− on the Na+ conductivity of NZSP was investigated computationally and experimentally. The Zn2+/F− co-assisting (Na3.3Zr1.85Zn0.15Si2PO12) solid-state electrolyte exhibits the ionic conductivity of 0.722 mS cm−1 at 30 °C, and the activation energy of ∼0.237 eV. Its applicability in a solid-state battery is tested, and the assembled Na/Na3V2(PO4)3 (NVP) battery exhibits an outstanding electrochemical performance of 98.4% capacity retention after being cycled at 0.5 C. Moreover, DFT calculations also have been used to demonstrate the effect of doping on the crystal structure and space migration energy barrier. This research provides new ideas for improving the electrochemical properties of inorganic solid electrolytes.