Microstructure-Dependent Charge/Discharge Behaviors of Hollow Carbon Spheres and its Implication for Sodium Storage Mechanism on Hard Carbon Anodes

Hard carbons are actively developed as a promising anode material for sodium ion batteries (SIBs). However, their sodium storage mechanism is poorly understood, leading to difficulties in design and development of high-performance hard carbon anode materials. In this work, hollow carbon spheres (HCSs) with different shell thickness as a model material to investigate the correlation between the microstructural change and resulting Na⁺ storage behavior during charge/discharge cycles are designed and synthesized. Ex situ X-ray diffraction and Raman evidences reveal that an interlayer spacing change of the graphitic nanodomains occurs in HCS electrode, leading to a shift of the reversible capacity from the high-potential sloping (HPS) region to the low-potential plateau (LPP) region. This unusual capacity shift suggests a microstructure-dependent Na⁺ storage reaction on the HCS electrode and can be well explained by "adsorption-intercalation" mechanism for these HCS materials. This work strengthens the understanding of the sodium storage behavior and provides a new perspective for the morphological and structural design of hard carbon anode materials for high-performance SIBs.