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.

Achieving both high redox activity and rapid ion transport is a critical and pervasive challenge in electrochemical energy storage applications. This challenge is significantly magnified when using large-sized charge carriers, such as the sustainable ammonium ion (NH₄⁺). A self-assembled MXene/n-type conjugated polyelectrolyte (CPE) superlattice-like heterostructure that enables redox-active, fast, and reversible ammonium storage is reported. The superlattice-like structure persists as the CPE:MXene ratio increases, accompanied by a linear increase in the interlayer spacing of MXene flakes and a greater overlap of CPEs. Concurrently, the redox activity per unit of CPE unexpectedly intensifies, a phenomenon that can be explained by the enhanced de-solvation of ammonium due to the increased volume of 3 Å-sized pores, as indicated by molecular dynamic simulations. At the maximum CPE mass loading (MXene:CPE ratio = 2:1), the heterostructure demonstrates the strongest polymeric redox activity with a high ammonium storage capacity of 126.1 C g⁻¹ and a superior rate capability at 10 A g⁻¹. This work unveils an effective strategy for designing tunable superlattice-like heterostructures to enhance redox activity and achieve rapid charge transfer for ions beyond lithium.