Improving the ionic conductivity of polymer electrolytes induced by ceramic nanowire fillers with abundant lithium vacancies

The addition of ceramic fillers is regarded as an effective strategy for enhancing the ionic conductivity of polymer electrolytes. However, particulate fillers typically fail to provide continuous conductive pathways and effective reinforcement. Herein, we report a ceramic nanowire filler with long-range interfacial conductivity and abundant lithium vacancies for a poly(ethylene oxide) (PEO)-based all-solid-state polymer electrolyte. LLZO nanowires (LLZO NWs) with a high aspect ratio are synthesized by combining sol-gel electrospinning and the multi-step process involving pre-oxidation, pre-sintering, and secondary sintering, resulting in a high tensile strength of the composite electrolyte (6.87 MPa). Notably, tantalum-aluminum co-substituted LLZO NWs (TALLZO NWs) release abundant lithium vacancies, further enhancing the Lewis acid-base properties, leading to a rapid ion migration speed (Li+ transfer number = 0.79) and significantly high ionic conductivity (3.80 x 10-4 S cm-1). Due to the synergistic effect of nanostructure modification and heteroatom co-doping, the assembled all-solid-state lithium-sulfur battery exhibits a high initial discharge capacity (776 mA h g-1 at 25 degrees C), remarkable rate capability, and excellent cycling performance (81% capacity retention after 200 cycles at 0.1C). The TALLZO NWs, characterized by a high aspect ratio and abundant lithium vacancies, enhance the coupling interactions among the PEO chains, TALLZO NWs, and LiTFSI. This interaction leads to a significant increase in ionic conductivity and Li+ transfer number for CPE.