One-Dimensional Oxide Nanostructures Possessing Reactive Surface Defects Enabled a Lithium-Rich Region and High-Voltage Stability for All-Solid-State Composite Electrolytes

The development of highly safe and low-cost solid polymer electrolytes for all-solid-state lithium batteries (ASSLBs) has been hindered by low ionic conductivity, poor stability under high-voltage conditions, and severe lithium-dendrite-induced short circuits. In this study, Li-doped MgO nanofibers bearing reactive surface defects of scaled-up production are introduced to the poly(ethylene oxide) (PEO)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) system. The characterizations and density functional theory calculations reveal that TFSI^- is strongly adsorbed on the nanofibers based on the electrostatic interactions of surface oxygen vacancies and the formation of Li-N and Li-O bonds derived from the exposed Li. Additionally, the introduced Li exposed near oxygen vacancies may be liberated from the lattice and engage in the formation of Li-rich domains. Therefore, a high ionic conductivity of 1.48 × 10^-4 S cm^-1 for the solid electrolyte at 30 °C and excellent cycling stability for the assembled battery, with a discharge capacity retention of 85.2% after 1500 cycles at 2C, can be achieved. Furthermore, the increased coordination of EO chains in the Li-rich region and chemical interactions with nanofibers substantially improve the antioxidant stability of the solid electrolyte, endowing the LiNi_0.8Co_0.1Mn_0.1O₂/Li battery with a long lifespan of more than 700 cycles. The results of this study suggest that the surface defects of 1D oxide nanostructures can substantially improve the Li⁺ diffusion kinetics. This study provides insight into the construction of Li-rich regions for high-voltage ASSLBs.