Surface Chemistry and Mesopore Dual Regulation by Sulfur‐Promised High Volumetric Capacity of Ti3C2Tx Films for Sodium‐Ion Storage

Electrochemical sodium‐ion storage has come out as a promising technology for energy storage, where the development of electrode material that affords high volumetric capacity and long‐term cycling stability remains highly desired yet a challenge. Herein, Ti3C2Tx (MXene)‐based films are prepared by using sulfur (S) as the mediator to modulate the surface chemistry and microstructure, generating S‐doped mesoporous Ti3C2Tx films with high flexibility. The mesoporous architecture offers desirable surface accessibility without significantly sacrificing the high density of Ti3C2Tx film. Meanwhile, the surface sulfur doping of Ti3C2Tx favors the diffusion of sodium ions. These merits are of critical importance to realize high volumetric capacity of the electrode material. As a consequence, as the freestanding electrode material for electrochemical sodium‐ion storage, the S‐doped mesoporous Ti3C2Tx film exhibits a high volumetric capacity of 625.6 mAh cm−3 at 0.1 A g−1, which outperforms that of many reported electrodes. Moreover, outstanding rate capability and excellent long‐term cycling stability extending 5000 cycles are achieved. The work opens the door for innovative design and rational fabrication of MXene‐based films with ultrahigh volumetric capacity for sodium‐ion storage.