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Due to the demand to upgrade from lithium-ion batteries (LIB), sodium-ion batteries (SIB) have been paid considerable attention for their high-energy, cost-effective, and sustainable battery system. Red phosphorus is one of the most promising anode candidates for SIBs, with a high theoretical specific capacity of 2596 mAh g −1  and in the discharge potential range of 0.01–0.8 V; however, it suffers from a low electrical conductivity, a substantial expansion of volume (~300%), and sluggish electron/ion kinetics. Herein, we have designed a well-defined electrode, which consists of red phosphorus, nanowire arrays encapsulated in the vertically aligned carbon nanotubes (P@C NWs), which were fabricated via a two-step, anodized-aluminum oxide template. The designed anode achieved a high specific capacity of 2250 mAh g −1  (87% of the theoretical capacity), and a stepwise analysis of the reaction behavior between sodium and red phosphorus was demonstrated, both of which have not been navigated in previous studies. We believe that our rational design of the red phosphorus electrode elicited the specific reaction mechanism revealed by the charge – discharge profiles, rendered excellent electrical conductivity, and accommodated volume expansion through the effective nano-architecture, thereby suggesting an efficient structure for the phosphorus anode to advance in the future.

Eliciting Specific Electrochemical Reaction Behavior by Rational Design of a Red Phosphorus Electrode for Sodium-Ion Batteries