Long‐Cycle‐Life Sodium‐Ion Battery Fabrication via a Unique Chemical Bonding Interface Mechanism

Titanates have been widely reported as anode materials for sodium-ion batteries (SIBs). However, their wide temperature suitability and cycle life remain fundamental issues that hinder their practical application. Herein, a novel hollow Na2 Ti3 O7 microsphere (H-NTO) with a unique chemically bonded NTO/C(N) interface is reported. Theoretical calculations demonstrated that the NTO/C(N) interface stabilizes the crystal structure, and the optimized interface enables the H-NTO anode to stably operate for 80 000 cycles in a conventional ester electrolyte with negligible capacity loss. Optimizing the electrolyte allows the H-NTO electrode to cycle stably for 200 calendar days without capacity degradation at -40 °C. The excellent cycling stability is attributed to the NTO/C(N) interface and the stable solid electrolyte interphase formed by the highly adaptable electrolyte/electrode interface. Titanate exhibits solvent co-intercalation behavior in ether-based electrolytes, and its robust structure ensures that it can adapt to large volume changes at low temperatures. This study provides a unique perspective on the long-cycle mechanism of titanate anodes and highlights the critical importance of manipulating the interfacial chemistry in SIBs, including the material and electrode/electrolyte interfaces.