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 LiNi0.8Co0.1Mn0.1O2/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.