The lithium and sodium storage performances of phosphorus and its hierarchical structure

Recent preparation of black phosphorene and subsequent discovery of its excellent optical and electronic properties have attracted great attention, and renewed interest to phosphorus. Recent researches have indicated that phosphorus structures are promising anodes for lithium-ion and sodium-ion batteries. A high theoretical capacity of 2,596 mAh·g⁻¹ was predicted for phosphorus according to the reaction of 3Li/Na + P → Li₃P/Na₃P. However, fast capacity degradation is accompanying with most phosphorus structures due to the low electronic conductivity and structural pulverization induced by large volume change in charging and discharging proceses. The electrochemical performances are significantly affected by the hierarchical structural design of phosphorus. A few reviews of phosphorus structures have been reported recently. However, no review about the electrochemical performances of phosphorus structures according to their hierarchical structures has been reported. First of all, phosphrus allotropes along with their structure and fundamental properties are briefly reviewed in this work. Secondly, the studies on lithiation/sodiation mechanism of red/black phosphorus are presented. Thirdly, a summary about the electrochemical performances of red/black phosphorus composites with different hierarchical structures is presented. Furthermore, the development challenges and future perspectives of phosphorus structures as anodes for LIBs and SIBs are discussed. [Figure not available: see fulltext.].