Red@Black phosphorus core–shell heterostructure with superior air stability for high-rate and durable sodium-ion battery

Heterostructured electrodes have gained increasing attentions owing to the synergistic effects from individual building components and the unique interfaces. However, rational design and controllable fabrication of high areal capacity and durable phosphorus-based heterostructure anode for industry remains a critical challenge. Herein, a new red@black phosphorus core–shell heterostructure anchored on three-dimensional N-doped graphene (RP@BP/3DNG) has been prepared via a facile one-step solvothermal strategy. As demonstrated by experimental data and theoretical calculations, RP@BP/3DNG shows a superior high electronic conductivity and an extremely low Na+ diffusion barrier due to the build-in filed at the RP@BP heterointerface, thus RP@BP/3DNG delivers an ultra-high areal capacity of 3.46 mAh cm−2 (1440.2 mAh/g at 0.05 A/g), impressive rate performance (521.3 mAh/g at 10.0 A/g) as well as unprecedented capacity retention rate of 89.3% after 1200 cycles at 10.0 A/g when evaluated as an anode for sodium ion batteries (SIBs). Furthermore, the internal electric field at the interfaces of RP@BP leads to the shift of electron cloud from BP to RP, which greatly suppresses the reaction activity of lone-pair electrons of BP atoms, and therefore RP@BP/3DNG shows much enhanced air stability. This work heralds a new insight for designing high-performance and stable P-based anodes for rechargeable batteries.