Few-Layer Antimonene: Anisotropic Expansion and Reversible Crystalline-Phase Evolution Enable Large-Capacity and Long-Life Na-Ion Batteries

Two-dimensional (2D) antimonene is a promising anode material in sodium-ion batteries (SIBs) because of its high theoretical capacity of 660 mAh g^-1 and enlarged surface active sites. However, its Na storage properties and sodiation/desodiation mechanism have not been fully explored. Herein, we propose the sodiation/desodiation reaction mechanism of 2D few-layer antimonene (FLA) based on results acquired by in situ synchrotron X-ray diffraction, ex situ selected-area electron diffraction, and theoretical simulations. Our study shows that the FLA undergoes anisotropic volume expansion along the a/b plane and exhibits reversible crystalline phase evolution (Sb ⇋ NaSb ⇋ Na₃Sb) during cycling. Density-functional theory calculations demonstrate that the FLA has a small Na-ion diffusion barrier of 0.14 eV. The FLA delivers a larger capacity of 642 mAh g^-1 at 0.1 C (1 C = 660 mA g^-1) and a high rate capability of 429 mAh g^-1 at 5 C and maintains a stable capacity of 620 mA g^-1 at 0.5 C with 99.7% capacity retention from the 10th to the 150th cycle. Considering the 660 mAh g^-1 theoretical capacity of Sb, the electrochemical utilization of Sb atoms of FLA is as high as 93.9% at a rate of 0.5 C for over 150 cycles, which is the highest capacity and Sb utilization ratio reported so far. Our study discloses the Na storage mechanism of 2D FLA, boosting promising applications of 2D materials for advanced SIBs.