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

Abstract 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 Na₂Ti₃O₇ 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.