A Black Phosphorus–Graphite Composite Anode for Li‐/Na‐/K‐Ion Batteries

• Published in: Angewandte Chemie International Edition Vol. 59; no. 6; pp. 2318 - 2322
• Main Authors: Jin, Hongchang, Wang, Haiyun, Qi, Zhikai, Bin, De‐Shan, Zhang, Taiming, Wan, Yangyang, Chen, Jiaye, Chuang, Chenghao, Lu, Ying‐Rui, Chan, Ting‐Shan, Ju, Huanxin, Cao, An‐Min, Yan, Wensheng, Wu, Xiaojun, Ji, Hengxing, Wan, Li‐Jun
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 03.02.2020
• Edition: International ed. in English
• Subjects: alkali metal ion batteries; Alkali metals; anode materials; Anodes; Batteries; black phosphorus; Chemical reactions; Comparative studies; Diffusion coefficient; Electrochemistry; Electrode materials; formation energy; Free energy; Gravimetry; Heat of formation; Ion currents; Ion diffusion; ion diffusion coefficient; Ion storage; Ions; Lithium; Metal ions; Phosphorus; Redox reactions; Sodium; Spectroscopy; anode materials; ion diffusion coefficient; black phosphorus; alkali metal ion batteries; formation energy
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201913129

Black phosphorus (BP) is a desirable anode material for alkali metal ion storage owing to its high electronic/ionic conductivity and theoretical capacity. In‐depth understanding of the redox reactions between BP and the alkali metal ions is key to reveal the potential and limitations of BP, and thus to guide the design of BP‐based composites for high‐performance alkali metal ion batteries. Comparative studies of the electrochemical reactions of Li+, Na+, and K+ with BP were performed. Ex situ X‐ray absorption near‐edge spectroscopy combined with theoretical calculation reveal the lowest utilization of BP for K+ storage than for Na+ and Li+, which is ascribed to the highest formation energy and the lowest ion diffusion coefficient of the final potassiation product K3P, compared with Li3P and Na3P. As a result, restricting the formation of K3P by limiting the discharge voltage achieves a gravimetric capacity of 1300 mAh g−1 which retains at 600 mAh g−1 after 50 cycles at 0.25 A g−1. Into the black: The energy‐storage properties of black phosphorus are reported for Li/Na/K ion batteries. BP shows the lowest utilization for K+ storage than for Na+ and Li+, which is ascribed to the highest formation energy and the lowest ion diffusion coefficient of the final potassiation product K3P compared with Li3P and Na3P.