Electrical Conductivity Adjustment for Interface Capacitive‐Like Storage in Sodium‐Ion Battery

Abstract Sodium‐ion battery (SIB) is significant for grid‐scale energy storage. However, a large radius of Na ions raises the difficulties of ion intercalation, hindering the electrochemical performance during fast charge/discharge. Conventional strategies to promote rate performance focus on the optimization of ion diffusion. Improving interface capacitive‐like storage by tuning the electrical conductivity of electrodes is also expected to combine the features of the high energy density of batteries and the high power density of capacitors. Inspired by this concept, an oxide‐metal sandwich 3D‐ordered macroporous architecture (3DOM) stands out as a superior anode candidate for high‐rate SIBs. Taking Ni‐TiO 2 sandwich 3DOM as a proof‐of‐concept, anatase TiO 2 delivers a reversible capacity of 233.3 mAh g −1 in half‐cells and 210.1 mAh g −1 in full‐cells after 100 cycles at 50 mA g −1 . At the high charge/discharge rate of 5000 mA g −1 , 104.4 mAh g −1 in half‐cells and 68 mAh g −1 in full‐cells can also be obtained with satisfying stability. In‐depth analysis of electrochemical kinetics evidence that the dominated interface capacitive‐like storage enables ultrafast uptaking and releasing of Na‐ions. This understanding between electrical conductivity and rate performance of SIBs is expected to guild future design to realize effective energy storage.