Sandwiched composite electrolyte with excellent interfacial contact for high-performance solid-state sodium-ion batteries.

Solid-state sodium-ion batteries have attracted significant attention due to their rich resources, high safety, and high energy density. However, the lower ionic conductivity and inferior interfacial contact between solid-state electrolytes (SSEs) and electrodes limit their practical applications. Herein, polyvinylideneuoride-co-hexauoropropylene (PVDF-HFP) membrane is selected and a novel sandwiched composite PVDF-HFP/Na2.5 Zr1.95 Ce0.05 Si2.2 P0.8 O11.3 F0.7 /PVDF-HFP (G-NZC0.05SPF0.7-G) SSEs is well designed. The ionic conductivity of Na3 Zr2 Si2 PO12 is enhanced by Ce4+ /F- co-doping. The effects of Ce4+ and F- doping on the crystal structure, density, and ionic conductivity for Na3 Zr2 Si2 PO12 are well investigated. The optimal NZC0.05SPF0.7 delivers a high ionic conductivity of 1.39 × 10-3 S cm-1 at 25 ℃. Moreover, the PVDF-HFP membrane can significantly enhance the interface compatibility between NZC0.05SPF0.7 and electrodes. The as-prepared G-NZC0.05SPF0.7-G exhibits a large ionic conductivity of 1.07 × 10-3 S cm-1 at 25 ℃, wide electrochemical stability window up to 4.5 V, high critical current density of 1.2 A cm-2 , and stable Na plating/stripping over 600 h at 0.3 A cm-2 . The solid-state Na0.67 Mn0.47 Ni0.33 Ti0.2 O2 /G-NZC0.05SPF0.7-G/Na battery delivers a remarkable cycling stability and rate capability at 25 ℃, indicating that the as-prepared G-NZC0.05SPF0.7-G has a promising application for solid-state SIBs. This study demonstrates an effective strategy to develop advanced solid-state electrolytes for solid-state SIBs.