Computational Approach To Reveal the Structural Stability and Electronic Properties of Lithiated M/CNT (M = Si, Ge) Nanocomposites as Anodes for Lithium-Ion Batteries

[Image: see text] This work is motivated to explore the structural stability and electronic and electrochemical properties of nanocomposites of M(4)Li(n) (M = Si and Ge)–carbon nanotube (CNT) by employing first-principles density functional theory calculations. By analyzing the structural stability of various M(4)Li(n) (n = 0–10) clusters, it is revealed that a tetrahedron-shaped M(4)Li(4) Zintl cluster is found to be highly stable. Our study on the interaction between the lithiated clusters and CNT illustrates that the charge transfer from the former to latter plays a pivotal role in stabilizing these nanocomposites. The structural stability of those nanocomposites arises as a consequence of bonding between lithiated clusters and CNT, which is mediated through the cation−π interaction. The strength of the interaction between them is well reflected in electronic structure calculations by shifting the energy levels with respect to the Fermi energy. Further, the electrochemical properties of these nanocomposites are explored by forming an assembly of the cluster-inserted CNT. The calculated average intercalation voltage of the systems is found to be low (maximum ∼1.0 V for M = Si and 1.05 V for M = Ge), which demonstrates their anodic behavior.