A first-principles study on Si24 as an anode material for rechargeable batteries

Abstract

Due to its intriguing geometry, possessing an open-channel structure, Si₂₄ demonstrates potential for storing and/or transporting Li/Na ions in rechargeable batteries. In this work, first-principles calculations were employed to investigate the phase stability and Li/Na storage and transport properties of the Si₂₄ anode to evaluate its electrochemical performance for batteries. The intercalation of Li and Na into the Si₂₄ structure could deliver a capacity of 159 mA h g⁻¹ (Li₄Si₂₄ and Na₄Si₂₄), and the average intercalation potentials were 0.17 V (vs. Li) and 0.34 V (vs. Na). Moreover, the volume change of Si₂₄ upon intercalation proved very small (0.09% for Li, 2.81% for Na), indicating its “zero-strain” properties with stable cycling performance. Li⁺ and Na⁺ can diffuse along the channels inside the Si₂₄ structure with barrier energies of 0.14 and 0.80 eV respectively, and the ionic conductivity of Li_2.66Si₂₄ was calculated to be as high as 1.03 × 10⁻¹ S cm⁻¹ at 300 K. Our calculations indicate that the fast Li-ionic conductivity properties make the Si₂₄ structure a novel anode material for both lithium and sodium ion batteries.