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Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes

Nature Nanotechnology volume 11, pages 626–632 (2016)Cite this article

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Abstract

Metallic lithium is a promising anode candidate for future high-energy-density lithium batteries. It is a light-weight material, and has the highest theoretical capacity (3,860 mAh g–1) and the lowest electrochemical potential of all candidates. There are, however, at least three major hurdles before lithium metal anodes can become a viable technology: uneven and dendritic lithium deposition, unstable solid electrolyte interphase and almost infinite relative dimension change during cycling. Previous research has tackled the first two issues, but the last is still mostly unsolved. Here we report a composite lithium metal anode that exhibits low dimension variation (∼20%) during cycling and good mechanical flexibility. The anode is composed of 7 wt% ‘lithiophilic’ layered reduced graphene oxide with nanoscale gaps that can host metallic lithium. The anode retains up to ∼3,390 mAh g–1 of capacity, exhibits low overpotential (∼80 mV at 3 mA cm–2) and a flat voltage profile in a carbonate electrolyte. A full-cell battery with a LiCoO2 cathode shows good rate capability and flat voltage profiles.

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Figure 1: Fabrication of a layered Li–rGO composite film.
Figure 2: Characterization of the materials.
Figure 3: Li deposition behaviour and in situ characterization.
Figure 4: Electrochemical characterization of the Li–rGO electrodes.
Figure 5: Electrochemical performance of the LCO/Li–rGO cells.

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References

  1. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  CAS  Google Scholar 

  2. Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    Article  CAS  Google Scholar 

  3. Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).

    Article  CAS  Google Scholar 

  4. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nature Mater. 11, 19–29 (2012).

    Article  CAS  Google Scholar 

  5. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    Article  CAS  Google Scholar 

  6. Yamaki, J.-i. et al. A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte. J. Power Sources 74, 219–227 (1998).

    Article  CAS  Google Scholar 

  7. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ionics 148, 405–416 (2002).

    Article  CAS  Google Scholar 

  8. Bieker, G., Winter, M. & Bieker, P. Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 17, 8670–8679 (2015).

    Article  CAS  Google Scholar 

  9. Peled, E. The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems—the solid electrolyte interphase model. J. Electrochem. Soc. 126, 2047–2051 (1979).

    Article  CAS  Google Scholar 

  10. Aurbach, D. et al. Attempts to improve the behavior of Li electrodes in rechargeable lithium batteries. J. Electrochem. Soc. 149, A1267–A1277 (2002).

    Article  CAS  Google Scholar 

  11. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).

    Article  CAS  Google Scholar 

  12. Bhattacharyya, R. et al. In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries. Nature Mater. 9, 504–510 (2010).

    Article  CAS  Google Scholar 

  13. Chandrashekar, S. et al. 7Li MRI of Li batteries reveals location of microstructural lithium. Nature Mater. 11, 311–315 (2012).

    Article  CAS  Google Scholar 

  14. Harry, K. J., Hallinan, D. T., Parkinson, D. Y., MacDowell, A. A. & Balsara, N. P. Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nature Mater. 13, 69–73 (2014).

    Article  CAS  Google Scholar 

  15. Lu, Y., Tu, Z. & Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nature Mater. 13, 961–969 (2014).

    Article  CAS  Google Scholar 

  16. Ota, H., Shima, K., Ue, M. & Yamaki, J.-i. Effect of vinylene carbonate as additive to electrolyte for lithium metal anode. Electrochim. Acta 49, 565–572 (2004).

    Article  CAS  Google Scholar 

  17. Ota, H., Sakata, Y., Wang, X., Sasahara, J. & Yasukawa, E. Characterization of lithium electrode in lithium imides/ethylene carbonate and cyclic ether electrolytes: II. surface chemistry. J. Electrochem. Soc. 151, A437–A446 (2004).

    Article  CAS  Google Scholar 

  18. Ding, F. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 135, 4450–4456 (2013).

    Article  CAS  Google Scholar 

  19. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nature Commun. 6, 6362 (2015).

    Article  CAS  Google Scholar 

  20. Crowther, O. & West, A. C. Effect of electrolyte composition on lithium dendrite growth. J. Electrochem. Soc. 155, A806–A811 (2008).

    Article  CAS  Google Scholar 

  21. Li, W. et al. The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth. Nature Commun. 6, 7436 (2015).

    Article  Google Scholar 

  22. Stone, G. M. et al. Resolution of the modulus versus adhesion dilemma in solid polymer electrolytes for rechargeable lithium metal batteries. J. Electrochem. Soc. 159, A222–A227 (2012).

    Article  CAS  Google Scholar 

  23. Bouchet, R. et al. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nature Mater. 12, 452–457 (2013).

    Article  CAS  Google Scholar 

  24. Bates, J. B., Dudney, N. J., Neudecker, B., Ueda, A. & Evans, C. D. Thin-film lithium and lithium-ion batteries. Solid State Ionics 135, 33–45 (2000).

    Article  CAS  Google Scholar 

  25. Kanno, R. & Murayama, M. Lithium ionic conductor thio-LISICON: the Li2S­GeS2­P2S5 system. J. Electrochem. Soc. 148, A742–A746 (2001).

    Article  CAS  Google Scholar 

  26. Kamaya, N. et al. A lithium superionic conductor. Nature Mater. 10, 682–686 (2011).

    Article  CAS  Google Scholar 

  27. Murugan, R., Thangadurai, V. & Weppner, W. Fast lithium ion conduction in garnet-type Li7La3Zr2O12 . Angew. Chem. Int. Ed. 46, 7778–7781 (2007).

    Article  CAS  Google Scholar 

  28. Zheng, G. et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes . Nature Nanotech. 9, 618–623 (2014).

    Article  CAS  Google Scholar 

  29. Yan, K. et al. Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode. Nano Lett. 14, 6016–6022 (2014).

    Article  CAS  Google Scholar 

  30. Iijima, S. & Ichihashi, T. Single-shell carbon nanotubes of 1-nm diameter. Nature 363, 603–605 (1993).

    Article  CAS  Google Scholar 

  31. Yu, M.-F. et al. Strength and breaking mechanism of multiwalled carbon nanotubes under tensile load. Science 287, 637–640 (2000).

    Article  CAS  Google Scholar 

  32. Novoselov, K. S. et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197–200 (2005).

    Article  CAS  Google Scholar 

  33. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183–191 (2007).

    Article  CAS  Google Scholar 

  34. Ying, J. Y., Mehnert, C. P. & Wong, M. S. Synthesis and applications of supramolecular-templated mesoporous materials. Angew. Chem. Int. Ed. 38, 56–77 (1999).

    Article  CAS  Google Scholar 

  35. Dahn, J. R., Zheng, T., Liu, Y. H. & Xue, J. S. Mechanisms for lithium insertion in carbonaceous materials. Science 270, 590–593 (1995).

    Article  CAS  Google Scholar 

  36. Ng, S. H., Wang, J., Guo, Z. P., Wang, G. X. & Liu, H. K. Single wall carbon nanotube paper as anode for lithium-ion battery. Electrochim. Acta 51, 23–28 (2005).

    Article  CAS  Google Scholar 

  37. Lee, S. W. et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nature Nanotech. 5, 531–537 (2010).

    Article  CAS  Google Scholar 

  38. Hu, L. B. et al. Silicon-carbon nanotube coaxial sponge as Li-ion anodes with high areal capacity. Adv. Energy Mater. 1, 523–527 (2011).

    Article  CAS  Google Scholar 

  39. Wang, H. L. et al. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability. Nano Lett. 11, 2644–2647 (2011).

    Article  CAS  Google Scholar 

  40. Liu, J. Charging graphene for energy. Nature Nanotech. 9, 739–741 (2014).

    Article  CAS  Google Scholar 

  41. Raccichini, R., Varzi, A., Passerini, S. & Scrosati, B. The role of graphene for electrochemical energy storage. Nature Mater. 14, 271–279 (2015).

    Article  CAS  Google Scholar 

  42. Son, I. H. et al. Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density. Nature Commun. 6, 7393 (2015).

    Article  CAS  Google Scholar 

  43. Zhou, G., Paek, E., Hwang, G. S. & Manthiram, A. Long-life Li/polysulphide batteries with high sulphur loading enabled by lightweight three-dimensional nitrogen/sulphur-codoped graphene sponge. Nature Commun. 6, 7760 (2015).

    Article  CAS  Google Scholar 

  44. Reddy, A. L. M. et al. Synthesis of nitrogen-doped graphene films for lithium battery application. Acs Nano 4, 6337–6342 (2010).

    Article  CAS  Google Scholar 

  45. Dikin, D. A. et al. Preparation and characterization of graphene oxide paper. Nature 448, 457–460 (2007).

    Article  CAS  Google Scholar 

  46. Sun, G. et al. Actuation triggered exfoliation of graphene oxide at low temperature for electrochemical capacitor applications. Carbon 68, 748–754 (2014).

    Article  CAS  Google Scholar 

  47. Gao, Y. et al. Popping of graphite oxide: application in preparing metal nanoparticle catalysts. Adv. Mater. 27, 4688–4694 (2015).

    Article  CAS  Google Scholar 

  48. Marcano, D. C. et al. Improved synthesis of graphene oxide. ACS Nano 4, 4806–4814 (2010).

    Article  CAS  Google Scholar 

  49. Ganguly, A., Sharma, S., Papakonstantinou, P. & Hamilton, J. Probing the thermal deoxygenation of graphene oxide using high-resolution in situ X-ray-based spectroscopies. J. Phys. Chem. C 115, 17009–17019 (2011).

    Article  CAS  Google Scholar 

  50. Aurbach, D. Nonaqueous Electrochemistry (CRC, 1999).

    Book  Google Scholar 

Download references

Acknowledgements

Y.C. acknowledges the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) program.

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Author notes

  1. Dingchang Lin and Yayuan Liu: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, 94305, California, USA

    Dingchang Lin, Yayuan Liu, Zheng Liang, Hyun-Wook Lee, Jie Sun, Kai Yan, Jin Xie & Yi Cui

  2. Department of Applied Physics, Stanford University, Stanford, 94305, California, USA

    Haotian Wang

  3. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, 94025, California, USA

    Yi Cui

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  1. Dingchang Lin
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Contributions

D.L., Y.L. and Y.C. conceived the idea and experiments. D.L. and Y.L. carried out the synthesis and performed the materials characterizations and electrochemical measurements. Z.L. assisted the electrochemical measurements. H.W.L. conducted in situ TEM characterization. J.S. performed the first-principles calculations. H.W. and K.Y. assisted in the Raman and XPS measurement. J.X. assisted the XPS analysis. D.L., Y.L. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yi Cui.

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Lin, D., Liu, Y., Liang, Z. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nature Nanotech 11, 626–632 (2016). https://doi.org/10.1038/nnano.2016.32

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