Functionalized MTiCT MXenes (M = Cr and Mo; T = F, O, and OH) as high performance electrode materials for sodium ion batteries.

First-principles calculations were performed to study the electrochemical performance of M2TiC2 (M = Cr or Mo) and M2TiC2Tx (T = O, F or OH) used as anode materials for sodium ion batteries (SIBs). The O functionalized MXenes (Cr2TiC2O2 and Mo2TiC2O2) are found to be more stable than F and OH terminated systems. The diffusion performance of sodium in MXene materials is mainly affected by the functional groups. The lowest diffusion barrier of functionalized MXenes is about one order larger in magnitude than that of bare MXenes. Although the introduction of O-groups hinders the diffusion of sodium, it can greatly improve the theoretical storage capacities. Meanwhile, the diffusion paths and diffusion energy barriers of Na are affected by Na concentration effects, while the interactions between terminations have little effect. Furthermore, multiple layers of sodium atoms are found to be adsorbed between the layers of M2TiC2O2, thus significantly increasing the theoretical capacities. The theoretical sodium storage capacities of M2TiC2O2 monolayers reach 515.70 mA h g-1 (M = Cr) and 362.46 mA h g-1 (M = Mo) and the OCVs can approach 0.034 V (M = Cr) and 0.042 V (M = Mo). Therefore, Cr2TiC2O2 and Mo2TiC2O2 are expected to be promising anode materials for SIBs due to their excellent properties, such as good electronic conductivity, low sodium diffusion barrier, and high theoretical sodium storage capacity.