The Dimensional Revolution of Phosphorus: From Allotropicity to Battery System Applications

Phosphorus‐based materials have emerged as promising high‐capacity anodes for next‐generation batteries due to their high theoretical capacity and suitable operating voltage. However, practical applications are hindered by intrinsic limitations such as poor electrical conductivity, significant volume expansion, and sluggish ion kinetics. This review presents an innovative dimension‐based classification framework, including zero‐dimensional (0D), one‐dimensional (1D), two‐dimensional (2D), and three‐dimensional (3D) phosphorus allotropes, to systematically explore the structural characteristics, synthesis methods, and electrochemical properties. We highlight the critical role of composite strategies, particularly with carbon and other functional materials, in mitigating the above challenges and enhancing electrochemical performance. The review provides a comprehensive analysis of phosphorus‐carbon composites, heteroatom doping, and interfacial design strategies for improving cycling stability and rate capability. Furthermore, we examine the synergistic effects of heterostructures formed between different phosphorus allotropes, which significantly improve charge transport, structural stability, and cycling durability. This review aims to provide an outlook for the current challenges and future directions for the development of phosphorus‐based electrodes in lithium‐ion, sodium‐ion, and potassium‐ion batteries, thus unlocking the potential of high‐performance phosphorus.