In situ establishment of rapid lithium transport pathways at the electrolytes-electrodes interface enabling dendrite-free and long-lifespan solid-state lithium batteries.

[Display omitted] Composite solid-state electrolytes (CSEs) exhibit the high ionic conductivity of ceramic electrolytes and the facile processing and good flexibility of polymer electrolytes, representing the most promising class of solid-state electrolytes for the industrialization of lithium batteries. Nevertheless, CSEs continue encountering substantial interfacial resistance, which impedes their practical deployment. In response to these issues, a Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 /poly(vinylidene fluoride) (LLZTO/PVDF) solid electrolyte membranes with a thickness of 25 μm were prepared by the doctor blade method. In situ polymerization of 1,3-dioxolane (DOL) at the electrolyte–electrode interface was initiated by lithium hexafluorophosphate (LiPF 6) and lithium difluoro(oxalate)borate (LiDFOB) dual-salts to produce poly(1,3-dioxolane) (PDOL). The presence of PDOL in LLZTO/PVDF@PDOL results in a high room temperature ionic conductivity of 3.578 mS cm−1. Moreover, the Li||LLZTO/PVDF@PDOL||LiFePO 4 (LFP) battery exhibits a discharge-specific capacity of 143 mAh g−1 and capacity retention of 81.7 % after 1000 cycles at 2 C, and the pouch cell with LLZTO/PVDF@PDOL achieved a high energy density of 190 Wh kg−1. The findings of this study may facilitate the industrial application of CSEs. [ABSTRACT FROM AUTHOR]