Effect of Interlayer Spaces and Interfacial Structures on High-Performance MXene/Ionic Liquid Supercapacitors: A Molecular Dynamics Simulation

The combination of high-capacitance MXenes and wide-electrochemical-window ionic liquids (ILs) has exhibited bright prospects in supercapacitors. Several strategies, such as surficial functionalization and interlayer spacing tuning, have been used to enhance the electrochemical performance of supercapacitors. However, the lack of theoretical guidance on these strategies, including the effects of the microenvironment in the interlayer of confined ILs, hindered the further exploration of such devices. Herein, we performed molecular dynamics simulations to comprehensively investigate the effects of the interlayer space and surface terminations of MXene electrodes on capacity. The results show that the electrical double layer (EDL) structure was found to form on the interface between the MXene electrode and ILs electrolyte by analyzing the ion number density and charge density in the nanometer confined spaces. Under the same potential, the -OH terminations significantly impact the ion orientation in the EDL, particularly near the electrode surface, where cations tend to align vertically, allowing the retention of more cations at the electrode surfaces. Interestingly, such an orientation distribution was decisively from the hydrogen bonds expressed by O-H···O between the -OH termination of MXene and -OH groups of ILs. The differential capacitances of the supercapacitors were calculated by the surficial electron density, and it showed that the capacitance is a nearly one-quarter increase in the 14 Å interlayer spacing compared with that of 10 Å under an applied potential of 2 V. At the same time, the Ti₃C₂(OH)₂ electrode had a higher differential capacitance than the Ti₃C₂O₂ electrode, which possibly originates from the stronger hydrogen bonds to contribute to the vertical aggregation of the cations. Our results highlighted the roles of the interlayer spacing distance and surface terminations of the MXene on the performance of the type of supercapacitor.