Tuning the Surface Stability and Li/Na Storage of MXenes by Controlling the Surface Termination Coverage

2D transition metal carbides and/or nitrides, MXenes, are a class of widely studied materials with great potential for energy storage applications. The control of surface chemistry is an effective approach for preparing novel MXenes and modifying their electrochemical properties. However, an in-depth and systematic atomic-scale study of the effect of surface termination on MXene stability and electrochemical performance is scarce and thus is highly desired. Here, through high-throughput first-principles calculations, 28 stable chalcogen-functionalized M₂CT_z (M = V, Nb, and Ta, T = S, Se, and Te) under different chemical environments are identified. The reduction of termination coverage improves electrical conductivity but weakens in-plane stiffness. Intriguingly, based on charge transfer mechanism, the diffusion barrier of lithium/sodium atoms on the M₂CT_z exhibits a volcano-like relationship with termination coverage, and the ion diffusion channel formed in half termination coverage greatly accelerates lithium ion diffusion and returns to or exceeds sodium ion diffusion rate at full termination coverage. V₂CSe₂/Nb₂CS_z not only displays the large lithium/sodium capacity (592/409-466 mAhg^-1) but also exhibits low barrier energy and open-circuit voltage, suggesting a promising candidate anode material for lithium/sodium-ion batteries. These findings provide insights into the design and fabrication of MXenes and tuning the electrochemical performance of MXenes by controlling termination coverage.