Calcium annealing approach to control of surface groups and formation of oxide in Ti Ti₃C₂T_x MXene

Ti₃C₂T_x MXene, a 2D material, is known to exhibit unique characteristics that are strongly dependent on surface termination groups. Here, we developed a novel annealing approach with Ca as a reducing agent to simultaneously remove F and O groups from the surface of multilayered MXene powder. Unlike H2 annealing that removes F effectively but has difficulty in removing O, annealing with Ca effectively removed both O and F. X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy revealed that the proposed approach effectively removed F and O from the MXene powder. The results of O/N analyses showed that the O concentration decreased by 57.5% (from 2.66 to 1.13 wt%). In addition, XPS fitting showed that the volume fraction of metal oxides (TiO₂ and Al₂O₃) decreased, while surface termination groups (–O and –OH) were enhanced, which could increase the hydrophilic and adsorption properties of the MXene. These findings suggest that when F and O are removed from the MXene powder, the interlayer spacing of its lattice structure increases. The proposed treatment also resulted in an increase in the specific surface area (from 5.17 to 10.98 m²/g), with an increase in oxidation resistance temperature in air from ~436 to ~667 °C. The benefits of this novel technology were verified by demonstrating the significantly improved cyclic charge–discharge characteristics of a lithium-ion battery with a Ca-treated MXene electrode.