Unraveling the Role of Metal Vacancy Sites and Doped Nitrogen in Enhancing Pseudocapacitance Performance of Defective MXene

Abstract Nitrogen‐doped titanium carbides (MXene) films exhibit extraordinary volumetric capacitance when high‐concentration sulfuric acid electrolyte is utilized owing to the enhancement of pseudocapacitance. However, the energy storage mechanism of nitrogen‐doped MXene is unclear due to the complex electrode structure and electrolyte ions’ behavior. Here, based on pristine MXene (Ti 3 C 2 O 2 ), three different MXene structures are constructed by introducing metal vacancy sites and doped nitrogen atoms, namely, defective MXene (Ti 2.9 C 2 O 2 ), nitrogen‐doped MXene (Ti 3 C 2 O 1.9 N 0.1 ), and nitrogen‐doped MXene with metal vacancy sites (Ti 2.9 C 2 O 1.9 N 0.1 ). Then, the density functional theory (DFT)‐based calculations coupled with the effective screening medium reference interaction site method (ESM‐RISM) are applied to reveal the electrochemical behavior at the electrode/electrolyte interfacial area. Through analyzing the electronic structure, electrical double‐layer capacitance (EDLC), and equilibrium potential of the pseudocapacitance reaction, the specific effect of structural changes on their performance can be clarified: metal vacancy sites can reduce the potential difference of gap layer (Outer Helmholtz plane) at charged state and increase the electronic capacity of Ti, which can be used to explain the high pseudocapacitance, low charge transfer resistance and high‐rate capacity properties of nitrogen‐doped MXene observed in experiments.