Enabling Electron Delocalization by Conductor Heterostructure for Highly Reversible Sodium Storage

Abstract Niobium oxides have fascinated numerous interests for ultrafast sodium‐ion batteries due to their impressive stability, fast pseudocapacitive kinetics, and high safety features. However, the poor intrinsic electronic conductivity and unrevealed mechanisms largely limit their further applications. Here, inspired by density functional theory (DFT) calculations, the introduction of conductor heterostructure (Nb₂O₅/NbSe₂) can largely decrease the bulk phase inserted energy of Na⁺ from 9.88 to −3.54 eV, as well as promote the delocalization of electron, greatly improving the electrical conductivity of Nb₂O₅. As expected, the as‐obtained orthorhombic niobium pentoxide (T‐Nb₂O_5‐x‐NbSe₂@C) delivers a high conductivity of 3.69 S cm⁻¹, exhibiting a great improvement of four orders magnitude than that of the parent Nb₂O₅ (1.87 × 10⁻⁴ S cm⁻¹). Impressively, T‐Nb₂O_5‐x‐NbSe₂@C possesses a high reversible capacity of 249 mAh g⁻¹ at 0.1 A g⁻¹, as well as excellent rate performance of 63 mAh g⁻¹ at 5.0 A g⁻¹, nearly twins the capacity of parent porous Nb₂O₅. Furthermore, the periodic evolutions of the main peaks for targeted electrodes during repeated charging/discharging processes have been further revealed by in situ XRD, demonstrating a highly reversible inserted/extracted storage mechanism of Na⁺. This work provides a novel method to improve the conductivity of materials by constructing conductor heterojunction.