LAUSR

Lithium‐ion battery (LIB) anodes using red phosphorus materials are promising with the advantages of high capacity, low price, and abundant reserves. However, the huge volume expansion (≈300%) of red phosphorus during the charge and discharge process significantly limits their application. Herein, superassembled red phosphorus nanorod/reduced graphene oxide microflower (RPN/rGF) composites are reported. The RPNs can accommodate huge volume expansion, shorten lithium‐ion transmission distances, and provide more conductive contacts, and the rGF serves as an electron pathway and buffers the RPN volume expansion. Experimental and finite element simulations prove the fixation of PC bonds in the RPN/rGF composite, thereby demonstrating a high capacity (1760 mA h g−1 at 0.3 C), remarkable rate capability (1073 mA h g−1 at 3 C), and great cyclability (1380 mA h g−1 at 0.3 C over 300 cycle). This work could shed light on the future development of red phosphorus composite materials for commercially viable lithium‐ion batteries.