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

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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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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References

  1. 1.

    Jiang, J.-W. & Park, H. S. Negative Poisson’s ratio in single-layer black phosphorus. Nat. Commun. 5, 4727 (2014).

  2. 2.

    Cai, Y., Zhang, G. & Zhang, Y.-W. Layer-dependent band alignment and work function of few-layer phosphorene. Sci. Rep. 4, 6677 (2014).

  3. 3.

    Ling, X. et al. Low-frequency interlayer breathing modes in few-layer black phosphorus. Nano Lett. 15, 4080–4088 (2015).

  4. 4.

    Reich, E. S. Phosphorene excites materials scientists. Nature 506, 19 (2014).

  5. 5.

    Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).

  6. 6.

    Petoukhoff, C. E. et al. Ultrafast charge transfer and enhanced absorption in MoS2–organic van der Waals heterojunctions using plasmonic metasurfaces. ACS Nano 10, 9899–9908 (2016).

  7. 7.

    Zhang, H. Ultrathin two-dimensional nanomaterials. ACS Nano 9, 9451–9469 (2015).

  8. 8.

    Sun, J. et al. Formation of stable phosphorus–carbon bond for enhanced performance in black phosphorus nanoparticle–graphite composite battery anodes. Nano Lett. 14, 4573–4580 (2014).

  9. 9.

    Sun, J. et al. A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries. Nat. Nanotech. 10, 980–985 (2015).

  10. 10.

    Xu, G.-L. et al. Nanostructured black phosphorus/Ketjenblack–multiwalled carbon nanotubes composite as high performance anode material for sodium-ion batteries. Nano Lett. 16, 3955–3965 (2016).

  11. 11.

    Lukatskaya, M. R., Dunn, B. & Gogotsi, Y. Multidimensional materials and device architectures for future hybrid energy storage. Nat. Commun. 7, 12647 (2016).

  12. 12.

    Peng, L., Zhu, Y., Chen, D., Ruoff, R. S. & Yu, G. Two-dimensional materials for beyond lithium ion batteries. Adv. Energy Mater. 6, 1600025 (2016).

  13. 13.

    Wang, X., Weng, Q., Yang, Y., Bando, Y. & Golberg, D. Hybrid two-dimensional materials in rechargeable battery applications and their microscopic mechanisms. Chem. Soc. Rev. 45, 4042–4073 (2016).

  14. 14.

    Kwon, H. et al. Ultrathin and flat layer black phosphorus fabricated by reactive oxygen and water rinse. ACS Nano 10, 8723–8731 (2016).

  15. 15.

    Verkade, J. G. & Quin, L. D. Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis (Wiley-VCH, Weinheim, 1987).

  16. 16.

    Smith, J. G. Organic Chemistry (McGraw-Hill, New York, 2013).

  17. 17.

    Liu, S. et al. Thickness-dependent Raman spectra, transport properties and infrared photoresponse of few-layer black phosphorus. J. Mater. Chem. C 3, 10974–10980 (2015).

  18. 18.

    Yu, X. et al. Elucidating surface redox charge storage of phosphorus-incorporated graphenes with hierarchical architectures. Nano Energy 15, 576–586 (2015).

  19. 19.

    Ma, G. et al. Phosphorus and oxygen dual-doped graphene as superior anode material for room-temperature potassium-ion batteries. J. Mater. Chem. A 5, 7854–7861 (2017).

  20. 20.

    Silberberg, M. S., Duran, R., Haas, C. G. & Norman, A. D. Chemistry: The Molecular Nature of Matter and Change (McGraw-Hill, New York, 2006)..

  21. 21.

    Kang, J. et al. Solvent exfoliation of electronic-grade, two-dimensional black phosphorus. ACS Nano 9, 3596–3604 (2015).

  22. 22.

    Edmonds, M. et al. Creating a stable oxide at the surface of black phosphorus. ACS Appl. Mater. Interfaces 7, 14557–14562 (2015).

  23. 23.

    Asensio, M. C. et al. Interfaces and heterostructures of van der Waals materials. J. Phys. Condens. Matter 28, 490301 (2016).

  24. 24.

    Novoselov, K., Mishchenko, A., Carvalho, A. & Neto, A. C. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).

  25. 25.

    Gao, Y., Liu, Q. & Xu, B. Lattice mismatch dominant yet mechanically tunable thermal conductivity in bilayer heterostructures. ACS Nano 10, 5431–5439 (2016).

  26. 26.

    Acerce, M., Voiry, D. & Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat. Nanotech. 10, 313–318 (2015).

  27. 27.

    Gao, Q., Demarconnay, L., Raymundo-Piñero, E. & Béguin, F. Exploring the large voltage range of carbon/carbon supercapacitors in aqueous lithium sulfate electrolyte. Energy Environ. Sci. 5, 9611–9617 (2012).

  28. 28.

    Wang, J., Polleux, J., Lim, J. & Dunn, B. Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanoparticles. J. Phys. Chem. C 111, 14925–14931 (2007).

  29. 29.

    Wen, Y. et al. Expanded graphite as superior anode for sodium-ion batteries. Nat. Commun. 5, 4033 (2014).

  30. 30.

    Griffin, J. M. et al. In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors. Nat. Mater. 14, 812–819 (2015).

  31. 31.

    Frank, O., Dresselhaus, M. S. & Kalbac, M. Raman spectroscopy and in situ Raman spectroelectrochemistry of isotopically engineered graphene systems. Acc. Chem. Res. 48, 111–118 (2015).

  32. 32.

    van den Beld, W. T. et al. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry. Sci. Rep. 7, 45080 (2017).

  33. 33.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

  34. 34.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999).

  35. 35.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).

  36. 36.

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).

  37. 37.

    Klimeš, J., Bowler, D. R. & Michaelides, A. Chemical accuracy for the van der Waals density functional. J. Phys. Condens. Matter 22, 022201 (2009).

  38. 38.

    Klimeš, J., Bowler, D. R. & Michaelides, A. Van der Waals density functionals applied to solids. Phys. Rev. B 83, 195131 (2011).

  39. 39.

    Aykol, M., Kim, S. & Wolverton, C. Van der Waals interactions in layered lithium cobalt oxides. J. Phys. Chem. C 119, 19053–19058 (2015).

  40. 40.

    Kim, S. et al. Layered-layered-spinel cathode materials prepared by a high-energy ball-milling process for lithium-ion batteries. ACS Appl. Mater. Interfaces 8, 363–370 (2015).

  41. 41.

    Chen, K.-S. et al. Comprehensive enhancement of nanostructured lithium-ion battery cathode materials via conformal graphene dispersion. Nano Lett. 17, 2539–2546 (2017).

  42. 42.

    Zhi, M., Xiang, C., Li, J., Li, M. & Wu, N. Nanostructured carbon–metal oxide composite electrodes for supercapacitors: a review. Nanoscale 5, 72–88 (2013).

  43. 43.

    Du, H., Lin, X., Xu, Z. & Chu, D. Recent developments in black phosphorus transistors. J. Mater. Chem. C 3, 8760–8775 (2015).

  44. 44.

    Cao, J. et al. Supercapacitor electrodes from the in situ reaction between two-dimensional sheets of black phosphorus and graphene oxide. ACS Appl. Mater. Interfaces 10, 10330–10338 (2018).

  45. 45.

    Yu, X. et al. Emergent pseudocapacitance of 2D nanomaterials. Adv. Energy Mater. 8, 1702930 (2018).

  46. 46.

    Hummers, W. S. Jr & Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339–1339 (1958).

  47. 47.

    Choi, B. G. et al. Solution chemistry of self-assembled graphene nanohybrids for high-performance flexible biosensors. ACS Nano 4, 2910–2918 (2010).

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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

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.

Competing interests

The authors declare no competing interests.

Correspondence to Ho Seok Park.

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Further reading

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.