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A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries

Abstract

Sodium-ion batteries have recently attracted significant attention as an alternative to lithium-ion batteries because sodium sources do not present the geopolitical issues that lithium sources might. Although recent reports on cathode materials for sodium-ion batteries have demonstrated performances comparable to their lithium-ion counterparts, the major scientific challenge for a competitive sodium-ion battery technology is to develop viable anode materials. Here we show that a hybrid material made out of a few phosphorene layers sandwiched between graphene layers shows a specific capacity of 2,440 mA h g−1 (calculated using the mass of phosphorus only) at a current density of 0.05 A g−1 and an 83% capacity retention after 100 cycles while operating between 0 and 1.5 V. Using in situ transmission electron microscopy and ex situ X-ray diffraction techniques, we explain the large capacity of our anode through a dual mechanism of intercalation of sodium ions along the x axis of the phosphorene layers followed by the formation of a Na3P alloy. The presence of graphene layers in the hybrid material works as a mechanical backbone and an electrical highway, ensuring that a suitable elastic buffer space accommodates the anisotropic expansion of phosphorene layers along the y and z axial directions for stable cycling operation.

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Figure 1: Mechanism of sodiation in black phosphorus.
Figure 2: Evidence of monolayer and few-layer phosphorene.
Figure 3: Physical characterization of the phosphorene–graphene hybrid structure.
Figure 4: Electrochemical characterization of the phosphorene–graphene anode for sodium-ion batteries.

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Acknowledgements

This work was supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under contract DE-AC02-76SF00515. H.W.L. acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology under NRF-2012R1A6A3A03038593.

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Y.C. and J.S. conceived and designed the experiments. J.S. performed sample fabrication, characterization and electrochemical measurements. H.W.L. participated in part of the experiments and conducted in situ TEM and HR-TEM characterization. J.S., M.P., H.W.L. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript. J.S. and H.W.L. contributed equally to this work.

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Correspondence to Yi Cui.

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Sun, J., Lee, HW., Pasta, M. et al. A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries. Nature Nanotech 10, 980–985 (2015). https://doi.org/10.1038/nnano.2015.194

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