Phosphorene by Design: Synthesis‐Driven Molecular Architecture for Electrochemical Ion Transport and Storage

ABSTRACT Phosphorene represents a programmable two‐dimensional platform in which synthesis dictates molecular architecture, enabling precise control over ion transport and storage mechanisms. This review establishes a design‐centric framework by linking tailored synthesis strategies, from exfoliation to vapor‐phase growth, to the construction of phosphorene allotropes with targeted structural merits. It is demonstrated how this synthesis‐driven architecture directly governs ion transport kinetics and supports multifunctional roles of phosphorene as high‐capacity anodes, polysulfide‐trapping cathodes, solid‐electrolyte modifiers, or interfacial stabilizers across rechargeable battery and supercapacitors. Moreover, this review systematically correlates material states, including defective, doped, and heterostructured phosphorene, with tailored ion diffusion behaviors that govern electrochemical kinetics. Finally, critical challenges are thoroughly analyzed, and some forward‐looking research directions are outlined, emphasizing integrated strategies in material stabilization, interface engineering, and scalable synthesis to unlock full potential of phosphorene in powering next‐generation energy storage devices.