Computational studies on electrochemical performances of doped and substituted $Ti_3C_2O_2$ MXene

TL;DR

This study uses DFT to analyze how doping and substitution affect the electrochemical performance of Ti3C2O2 MXene electrodes, revealing doping enhances capacitance mainly through surface redox activity, while substitution degrades performance.

Contribution

It provides a detailed computational analysis of doping versus substitution effects on Ti3C2O2 MXene's electrochemical properties, highlighting doping as a promising strategy for capacitance enhancement.

Findings

Nitrogen doping at functional sites yields the highest capacitance.

Doping enhances pseudocapacitance via surface redox activity.

Substitution reduces electrochemical performance compared to pristine MXene.

Abstract

Using Density functional theory (DFT) in conjunction with a solvation model we have investigated the phenomenon of eletrode-electrolyte interaction at the electrode surface and its consequences on the electrochemical properties like the charge storage and total capacitance of doped and substituted oxygen functionalised Ti$_{3}$C$_{2}$ supercapcitor electrode. We have studied nitrogen doped, nitrogen substituted and molybdenum substituted Mxenes in acidic electrolyte H$_{2}$SO$_{4}$ solution. By considering nitrogen doping at different sites, we found that the greatest capacitance is obtained for doping at functional sites. Our results agree well with the available experiment. We also found that the enhancement in capacitances due to nitrogen doping is due to amplifications in the pseudocapcitances. We propose that the primary mechanism leading to the enhanced value of the capacitances due to nitrogen doping is surface redox activity. The performances for substituted systems, on the other hand, are degraded in comparison to the pristine ones. This suggests that better storage capacities in Ti$_3$C$_{2}$O$_{2}$ electrode can be obtained by doping only. We provide insights into the reasons behind contrasting behaviour in doped and substituted systems and suggest ways to further improve the capacitances in doped system.