Understanding the Lithium Storage Mechanism of Ti₃C₂T_<i>x</i> MXene

MXenes, as an emerging family of conductive two-dimensional materials, hold promise for late-model electrode materials in Li-ion batteries. A primary challenge hindering the development of MXenes as electrode materials is that a complete understanding of the intrinsic storage mechanism underlying the charge/discharge behavior remains elusive. This article presents two key discoveries: first, the characteristics of the Ti3C2Tx structure can be modified systematically by calcination in various atmospheres, and second, these structural changes greatly affect Li-ion storage behavior, which reveals the mechanism for lithium storage in Ti3C2Tx MXene. Specifically, via ammonization, the interlayer spacing gets dilated and uniform, giving rise to only one redox couple. In stark contrast, there are two well-recognized redox couples corresponding to two interlayer spacings in pristine Ti3C2Tx MXene, in which Li-ion (de)­intercalation occurs between interlayers in a sequential manner as evidenced by ex situ X-ray diffraction (XRD). Notably, the XRD diffraction peaks shift hardly in the whole range of charge/discharge voltage, indicating a zero-strain feature upon Li-ion (de)­intercalation. Moreover, the diffusion-controlled contribution percentage to capacity inversely depends on the scan rate. The understanding suggests a new design principle of the MXene anode: reduced lateral size to shorten the diffusion path and dilated interlayer spacing