Amorphous Zinc Phosphate Stabilizes Black Phosphorus Anodes for High‐Performance Lithium‐Ion Batteries

Abstract Black phosphorus (BP) is a promising anode material for lithium‐ion batteries (LIBs) due to its high theoretical capacity and favorable lithiation potential. However, practical implementation of BP is hindered by its low electrical conductivity, significant volumetric expansion during cycling, and the dissolution of lithium polyphosphides (LiPPs), all of which contribute to rapid capacity degradation. To address these challenges, the utilization of amorphous zinc phosphate (ZPO) as a multifunctional modifier is proposed. Featuring isotropic properties and abundant structural defects, amorphous ZPO effectively suppresses volume changes during cycling. Density functional theory calculations coupled with experimental analyses confirm that amorphous ZPO exhibits strong adsorptive interactions with LiPPs and alleviates the shuttle effect. Furthermore, it accelerates the decomposition of fluoroethylene carbonate, facilitating the formation of a stable, fluoride‐rich solid‐electrolyte interphase. As a result, the BP anode modified with amorphous ZPO demonstrates excellent electrochemical performance, achieving a capacity retention rate of 86% after 300 cycles at a high current rate of 4C, significantly outperforming conventional carbon‐based modification strategies. These results demonstrate that amorphous ZPO plays a crucial role in stabilizing BP‐based anodes, unlocking their potential for high‐rate and durable LIBs.