Wet‐Chemical Synthesis of Hollow Red‐Phosphorus Nanospheres with Porous Shells as Anodes for High‐Performance Lithium‐Ion and Sodium‐Ion Batteries

Large‐volume‐expansion‐induced material pulverization severely limits the electrochemical performance of red phosphorous (P) for energy‐storage applications. Hollow nanospheres with porous shells are recognized as an ideal structure to resolve these issues. However, a chemical synthetic approach for preparing nanostructured red P is always of great challenge and hollow nanosphere structures of red P have not yet been fabricated. Herein, a wet solvothermal method to successfully fabricate hollow P nanospheres (HPNs) with porous shells via a gas‐bubble‐directed formation mechanism is developed. More importantly, due to the merits of the porous and hollow structures, these HPNs reveal the highest capacities (based on the weight of electrode materials) of 1285.7 mA h g −1 for lithium‐ion batteries and 1364.7 mA h g −1 for sodium‐ion batteries at 0.2 C, and excellent long‐cycling performance.