Hierarchical Ion/Electron Networks Enable Efficient Red Phosphorus Anode with High Mass Loading for Sodium Ion Batteries

Abstract Red phosphorus (RP), with high theoretical specific capacity and low working potential, has been regarded as one of the most promising anodes for high‐performance sodium‐ion batteries (SIBs). However, the unsatisfactory performance of RP anodes especially under high mass loading conditions severely limited the development for practical applications, due to its large volume variations during cycling processes, and the poor electronic and ionic conductivity. Here, a hierarchical WDC/CNTs@RP electrode with high mass loadings of RP (up to 14.1 mg cm⁻²) and superior conductivity is rationally designed for both ions and electrons. Such unique hierarchical structures enable an unprecedented rate performance (1.63 mAh cm⁻² under 106.6 mA cm⁻²), long cycling life, and a decent gravimetric capacity of 468.88 mA h g⁻¹ based on the whole electrode and inactive components. This work presents an essential step toward practical applications of RP anode materials for SIBs batteries.