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Revealing molecular-level surface redox sites of controllably oxidized black phosphorus nanosheets

Nature Materials volume 18, pages 156–162 (2019)Cite this article

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Abstract

Bulk and two-dimensional black phosphorus are considered to be promising battery materials due to their high theoretical capacities of 2,600 mAh g−1. However, their rate and cycling capabilities are limited by the intrinsic (de-)alloying mechanism. Here, we demonstrate a unique surface redox molecular-level mechanism of P sites on oxidized black phosphorus nanosheets that are strongly coupled with graphene via strong interlayer bonding. These redox-active sites of the oxidized black phosphorus are confined at the amorphorized heterointerface, revealing truly reversible pseudocapacitance (99% of total stored charge at 2,000 mV s−1). Moreover, oxidized black-phosphorus-based electrodes exhibit a capacitance of 478 F g–1 (four times greater than black phosphorus) with a rate capability of ~72% (compared to 21.2% for black phosphorus) and retention of ~91% over 50,000 cycles. In situ spectroelectrochemical and theoretical analyses reveal a reversible change in the surface electronic structure and chemical environment of the surface-exposed P redox sites.

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Fig. 1: Chemical structure and interaction of the foBG hybrid.
Fig. 2: Morphology and microstructure of the foBG hybrid.
Fig. 3: Electrochemical characterizations of the foBG hybrid.
Fig. 4: Pseudocapacitive features of the foBG hybrid.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. The data are not publicly available due to restrictions (for example, information that could compromise the privacy of research participants).

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Acknowledgements

This work was supported by the R&D Convergence Program (CAP-15-02-KBSI) of the National Research Council of Science & Technology, the National Research Foundation funded by the Ministry of Science, ICT, and Future Planning (no. 2017M2A2A6A01021187) and the Energy Technology Development Project (ETDP) funded by the Ministry of Trade, Industry, and Energy (20172410100150), Republic of Korea. The authors thank the Korea Basic Science Institute for technical support and Y. Gogotsi for valuable discussions. S.K. and C.W. (DFT calculations) were supported by financial assistance award no. 70NANB14H012 from the US Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD). This research was supported in part through the computational resources and staff contributions of the Quest High Performance Computing Facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. S.K. is grateful for discussions with V. I. Hegde, M. Liu and S. Hao at Northwestern University.

Author information

Author notes

  1. Xu Yu

    Present address: School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, China

  2. These authors contributed equally: Puritut Nakhanivej, Xu Yu.

Authors and Affiliations

  1. School of Chemical Engineering, College of Engineering, Sungkyunkwan University, Suwon, Republic of Korea

    Puritut Nakhanivej, Xu Yu, Sul Ki Park & Ho Seok Park

  2. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Soo Kim & Chris Wolverton

  3. Research and Technology Center, Robert Bosch LLC, Cambridge, MA, USA

    Soo Kim

  4. Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA, USA

    Jin-Yong Hong & Jing Kong

  5. Carbon Industry Frontier Research Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon, Republic of Korea

    Jin-Yong Hong

  6. Division of Material Science, Korea Basic Science Institute, Daejeon, Republic of Korea

    Hae Jin Kim

  7. Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Wanju, Republic of Korea

    Wonki Lee & Jun Yeon Hwang

  8. Department of Materials Science & Metallurgy, University of Cambridge, Cambridge, UK

    Ji Eun Yang & Manish Chhowalla

  9. SKKU Advanced Institute of Nanotechnology (SAINT), College of Engineering & Department of Health Sciences and Technology, Samsung Advanced Institute for Health Sciences and Technology (SAIHST), Sungkyunkwan University, Suwon, Republic of Korea

    Ho Seok Park

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Contributions

H.S.P., P.N. and X.Y. conceived and designed the experiments. P.N. and X.Y. performed sample fabrication, characterization and electrochemical measurements. P.N. and X.Y. conducted in situ Raman spectroscopy and analysed in situ Raman and in situ NMR data. S.K.P. and H.J.K. carried out in situ NMR spectroscopy. J.-Y.H., J.E.Y., J.K. and M.C. characterized bulk and 2D BP and interpreted data. W.L. and J.Y.H. carried out HAADF-STEM and EDS measurements. S.K. and C.W. performed DFT calculations and data analysis. P.N., X.Y., S.K., M.C. and H.S.P. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Ho Seok Park.

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Nakhanivej, P., Yu, X., Park, S.K. et al. Revealing molecular-level surface redox sites of controllably oxidized black phosphorus nanosheets. Nature Mater 18, 156–162 (2019). https://doi.org/10.1038/s41563-018-0230-2

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