Confined Amorphous Red Phosphorus in MOF‐Derived N‐Doped Microporous Carbon as a Superior Anode for Sodium‐Ion Battery

Red phosphorus (P) has attracted intense attention as promising anode material for high-energy density sodium-ion batteries (NIBs), owing to its high sodium storage theoretical capacity (2595 mAh g^-1 ). Nevertheless, natural insulating property and large volume variation of red P during cycling result in extremely low electrochemical activity, leading to poor electrochemical performance. Herein, the authors demonstrate a rational strategy to improve sodium storage performance of red P by confining nanosized amorphous red P into zeolitic imidazolate framework-8 (ZIF-8) -derived nitrogen-doped microporous carbon matrix (denoted as P@N-MPC). When used as anode for NIBs, the P@N-MPC composite displays a high reversible specific capacity of ≈600 mAh g^-1 at 0.15 A g^-1 and improved rate capacity (≈450 mAh g^-1 at 1 A g^-1 after 1000 cycles with an extremely low capacity fading rate of 0.02% per cycle). The superior sodium storage performance of the P@N-MPC is mainly attributed to the novel structure. The N-doped porous carbon with sub-1 nm micropore facilitates the rapid diffusion of organic electrolyte ions and improves the conductivity of the encapsulated red P. Furthermore, the porous carbon matrix can buffer the volume change of red P during repeat sodiation/desodiation process, keeping the structure intact after long cycle life.