Enabling Fast Na+ Transfer Kinetics in the Whole‐Voltage‐Region of Hard‐Carbon Anodes for Ultrahigh‐Rate Sodium Storage

Efficient electrode materials, that combine high power and high energy, are the crucial requisites of sodium-ion batteries (SIBs), which have unwrapped new possibilities in the areas of grid-scale energy storage. Hard carbons (HCs) are considered as the leading candidate anode materials for SIBs, however, the primary challenge of slow charge-transfer kinetics at the low potential region (<0.1 V) remains unresolved till date, and the underlying structure-performance correlation is under debate. Herein, ultrafast sodium storage in the whole-voltage-region (0.01-2 V), with the Na⁺ diffusion coefficient enhanced by 2 orders of magnitude (≈10^-7 cm² s^-1 ) through rationally deploying the physical parameters of HCs using a ZnO-assisted bulk etching strategy is reported. It is unveiled that the Na⁺ adsorption energy (E_a ) and diffusion barrier (E_b ) are in a positive and negative linear relationship with the carbon p-band center, respectively, and balance of E_a and E_b is critical in enhancing the charge-storage kinetics. The charge-storage mechanism in HCs is evidenced through comprehensive in(ex) situ techniques. The as prepared HCs microspheres deliver a record high rate performance of 107 mAh g^-1 @ 50 A g^-1 and unprecedented electrochemical performance at extremely low temperature (426 mAh g^-1 @ -40 °C).