Nanoscale Surface and Bulk Electronic Properties of Ti3C2Tx MXene Unraveled by Multimodal X‐Ray Spectromicroscopy

Abstract 2D layered materials, such as transition metal carbides or nitrides, known as MXenes, offer an ideal platform to investigate charge transfer processes in confined environment, relevant for energy conversion and storage applications. Their rich surface chemistry plays an essential role in the pseudocapacitive behavior of MXenes. However, the local distribution of surface functional groups over single flakes and within few‐ or multilayered flakes remains unclear. In this work, scanning X‐ray microscopy (SXM) is introduced with simultaneous transmission and electron yield detection, enabling multimodal nanoscale chemical imaging with bulk and surface sensitivity, respectively, of individual MXene flakes. The Ti chemical bonding environment is found to significantly vary between few‐layered hydrofluoric acid‐etched Ti 3 C 2 T x MXenes and multilayered molten salt (MS)‐etched Ti 3 C 2 T x MXenes. Postmortem analysis of MS‐etched Ti 3 C 2 T x electrodes cycled in a Li‐ion battery further illustrates that simultaneous bulk and surface chemical imaging using SXM offers a method well adapted to the characterization of the electrode‐electrolyte interactions at the nanoscale.