Two-dimensional (2D) materials offer distinct advantages for electrochemical energy storage (EES) compared to bulk materials, including a high surface-to-volume ratio, tunable interlayer spacing, and excellent in-plane conductivity, making them highly attractive for applications in batteries and supercapacitors. Gaining a fundamental understanding of the energy storage processes in 2D material-based EES devices is essential for optimizing their chemical composition, surface chemistry, morphology, and interlayer structure to enhance ion transport, promote redox reactions, suppress side reactions, and ultimately improve overall performance. This review provides a comprehensive overview of the characterization techniques employed to probe charge storage mechanisms in 2D and thin-layered material-based EES systems, covering optical spectroscopy, imaging techniques, X-ray and neutron-based methods, mechanical probing, and nuclear magnetic resonance spectroscopy. We specifically highlight the application of these techniques in elucidating ion transport dynamics, tracking redox processes, identifying degradation pathways, and detecting interphase formation. Furthermore, we discuss the limitations, challenges, and potential pitfalls associated with each method, as well as future directions for advancing characterization techniques to better understand and optimize 2D material-based electrodes.

Understanding energy storage mechanisms in electrochemical energy storage devices lays the foundations for improving their energy and power density. Here we introduce in situ ultraviolet–visible (UV–Vis) spectroscopy method to distinguish battery-type, pseudocapacitive and electrical double-layer charge storage processes. On the basis of Ti₃C₂T_x MXene in aqueous acidic and neutral electrolytes, and lithium titanium oxide in an organic electrolyte, we found a correlation between the evolution of UV–Vis spectra and the charge storage mechanism. The electron transfer number for Ti₃C₂T_x in an acidic electrolyte was calculated using quantitative analysis, which was close to previous measurements using X-ray absorption spectroscopy. Further, we tested the methodology to distinguish the non-Faradaic process in Ti₃C₂T_x MXene in a water-in-salt electrolyte, despite well-defined peaks in cyclic voltammograms. In situ UV–Vis spectroscopy is a fast and cost-effective technique that effectively supplements electrochemical characterization to track changes in oxidation state and materials chemistry and determine the charge storage mechanism.