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The durable red phosphorus (RP) anode for lithium-ion batteries (LIBs) has attracted great attention owing to its high theoretical specific capacity (2596 mA·h·g−1) and moderate lithiation potential (∼ 0.7 V vs. Li+/Li). However, its intrinsic poor electrical conductivity, enormous volume expansion, and soluble intermediates (lithium polyphosphides, LixPPs) lead to poor cycling performance. To overcome these issues, we introduce a new type of wrinkle carbon spheres as the host for loading phosphorus through a vaporization—condensation strategy. Density functional theory calculations reveal that the wrinkle carbon sphere shows strong binding energy with P4 molecule, accelerating the adsorption and polymerization of P4, thus enhancing RP conversion in the preparation process. In the lithiation/delithiation process, the wrinkle carbon has strong bonding with phosphorus and strong adsorption with LixPPs, resulting in excellent cycling performance. The design strategy to modify RP polymerization via reforming the interaction between wrinkle carbon spheres and phosphorus expands the application of RP for LIBs and beyond. [ABSTRACT FROM AUTHOR]

Phosphorus anodes are a promising for fast‐charging high‐energy lithium‐ion batteries because of their high specific capacity (2596 mAh g–1) and suitable lithiation potential (0.7 V vs Li+/Li). To solve the large volumetric change and inherent poor electrical conductivity, various carbon‐based materials have been studied for loading P. However, the local aggregation of Li ions and electrons in P particles especially in the fast‐charging process induces an uneven lithiation reaction and the great transient stress, leading to poor fast‐charging performance. Herein, bismuth nanoparticles are implanted into a P/graphite (P/C) composite using ball milling. The Bi anode works as a small Li reservoir for trapping Li in the lithiation process and emitting Li in delithiation process prior to P anode, because the Bi anode has a starting lithiation/delithiation potential that is a little bit higher/lower than the P anode. Moreover, the low Li diffusion barrier in Bi and the stable interface between Bi and P enhance the Li reservoir effect of Bi, which promotes fast and uniform lithiation/delithiation reactions and avoids continuous cracking of the Bi‐P/C electrode. Therefore, the Bi‐P/C anode provides a high fast‐charging capacity of 1755.7 mAh g–1 at 7.8 A g–1 (5.2 C) and a high capacity retention of 86.3% after 300 cycles. [ABSTRACT FROM AUTHOR]