Liquid‐Phase Exfoliation of Non‐Van Der Waals Crystals into Nanoflakes for Energy Applications

Recently, 2D materials have emerged as a focal point in materials science research. Conventional 2D systems predominantly derive from layered van der Waals (vdW) crystals, where individual atomic planes are held together by weak interlayer interactions. However, groundbreaking developments have challenged this paradigm through the successful isolation of 2D materials from non‐van der Waals (non‐vdW) bulk crystals. Non‐vdW 2D materials resemble their vdW counterparts in atomically thin sheets with strong in‐plane covalent/ionic bonding but manifest distinguished structural characteristics, including large lattice distortions, abundant dangling bonds, and coordinatively unsaturated surface atoms. These intrinsic features endow them with enhanced surface reactivity and dynamic electronic states, which promote chemisorption of reactive species and accelerate interfacial charge transfer kinetics‐properties that are highly advantageous for energy applications. Nevertheless, the absence of weak interlayer vdW forces poses significant challenges in exfoliation processes, with fundamental mechanisms remaining poorly understood. This review systematically examines state‐of‐the‐art liquid‐phase exfoliation (LPE) methodologies for non‐vdW nanoflakes synthesis, critically analyzing their mechanistic foundations, process‐structure‐property relationships, and performance benchmarks in energy‐related technologies. Furthermore, key challenges are identified in improving nanoflakes quality, precise kinetic control, and advancing next‐generation artificial intelligence (AI) and smart energy systems, while proposing interdisciplinary strategies to advance this burgeoning field.