Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth

Abstract

Lithium metal is an attractive anode material for rechargeable batteries, owing to its high theoretical specific capacity of 3,860 mAh g−1. Despite extensive research efforts, there are still many fundamental challenges in using lithium metal in lithium-ion batteries. Most notably, critical information such as its nucleation and growth behaviour remains elusive. Here we explore the nucleation pattern of lithium on various metal substrates and unravel a substrate-dependent growth phenomenon that enables selective deposition of lithium metal. With the aid of binary phase diagrams, we find that no nucleation barriers are present for metals exhibiting a definite solubility in lithium, whereas appreciable nucleation barriers exist for metals with negligible solubility. We thereafter design a nanocapsule structure for lithium metal anodes consisting of hollow carbon spheres with nanoparticle seeds inside. During deposition, the lithium metal is found to predominantly grow inside the hollow carbon spheres. Such selective deposition and stable encapsulation of lithium metal eliminate dendrite formation and enable improved cycling, even in corrosive alkyl carbonate electrolytes, with 98% coulombic efficiency for more than 300 cycles.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Overpotential during Li deposition on various substrates.
Figure 2: Patterned deposition of Li metal.
Figure 3: Synthesis and characterization of hollow nanocapsules for Li metal.
Figure 4: Electrochemical performance of Li metal nanocapsules.

References

  1. 1

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

    Article  Google Scholar 

  2. 2

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

    Article  Google Scholar 

  3. 3

    Whittingham, M. S. History, evolution, and future status of energy storage. Proc. IEEE 100, 1518–1534 (2012).

    Article  Google Scholar 

  4. 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  Google Scholar 

  5. 5

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

    Article  Google Scholar 

  6. 6

    Whittingham, M. S. Electrical energy storage and intercalation chemistry. Science 192, 1126–1127 (1976).

    Article  Google Scholar 

  7. 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 Ion. 148, 405–416 (2002).

    Article  Google Scholar 

  8. 8

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

    Article  Google Scholar 

  9. 9

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

    Article  Google Scholar 

  10. 10

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

    Article  Google Scholar 

  11. 11

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

    Article  Google Scholar 

  12. 12

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

    Article  Google Scholar 

  13. 13

    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  Google Scholar 

  14. 14

    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  Google Scholar 

  15. 15

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

    Article  Google Scholar 

  16. 16

    Huggins, R. Advanced Batteries 123–149 (Springer, 2009).

    Google Scholar 

  17. 17

    Aurbach, D., Weissman, I., Schechter, A. & Cohen, H. X-ray photoelectron spectroscopy studies of lithium surfaces prepared in several important electrolyte solutions. A comparison with previous studies by Fourier transform infrared spectroscopy. Langmuir 12, 3991–4007 (1996).

    Article  Google Scholar 

  18. 18

    López, C. M., Vaughey, J. T. & Dees, D. W. Morphological transitions on lithium metal anodes. J. Electrochem. Soc. 156, A726 (2009).

    Article  Google Scholar 

  19. 19

    Aurbach, D. Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89, 206–218 (2000).

    Article  Google Scholar 

  20. 20

    Visco, S., Nimon, Y. & Katz, B. Compositions and methods for protection of active metal anodes and polymer electrolytes. US patent 20040131944 A1 (2004).

  21. 21

    La Mantia, F., Wessells, C. D., Deshazer, H. D. & Cui, Y. Reliable reference electrodes for lithium-ion batteries. Electrochem. Commun. 31, 141–144 (2013).

    Article  Google Scholar 

  22. 22

    Obrovac, M. N. & Christensen, L. Structural changes in silicon anodes during lithium insertion/extraction. Electrochem. Solid-State Lett. 7, A93 (2004).

    Article  Google Scholar 

  23. 23

    McDowell, M. T., Lee, S. W., Nix, W. D. & Cui, Y. 25th anniversary article: understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries. Adv. Mater. 25, 4966–4985 (2013).

    Article  Google Scholar 

  24. 24

    McDowell, M. T. et al. In situ TEM of two-phase lithiation of amorphous silicon nanospheres. Nano Lett. 13, 758–764 (2013).

    Article  Google Scholar 

  25. 25

    Hulteen, J. C. et al. Nanosphere lithography: size-tunable silver nanoparticle and surface cluster arrays. J. Phys. Chem. B 103, 3854–3863 (1999).

    Article  Google Scholar 

  26. 26

    Liu, N. et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotech. 9, 187–192 (2014).

    Article  Google Scholar 

  27. 27

    Liu, Y., Goebl, J. & Yin, Y. Templated synthesis of nanostructured materials. Chem. Soc. Rev. 42, 2610–2653 (2013).

    Article  Google Scholar 

  28. 28

    Li, N. et al. Sol-gel coating of inorganic nanostructures with resorcinol-formaldehyde resin. Chem. Commun. 49, 5135–5137 (2013).

    Article  Google Scholar 

  29. 29

    Liu, J. et al. Extension of the Stöber method to the preparation of monodisperse resorcinol-formaldehyde resin polymer and carbon spheres. Angew. Chem. Int. Ed. Engl. 50, 5947–5951 (2011).

    Article  Google Scholar 

  30. 30

    Zeng, Z., Liang, W.-I., Chu, Y.-H. & Zheng, H. In situ TEM study of the Li–Au reaction in an electrochemical liquid cell. Faraday Discuss. 176, 95–107 (2014).

    Article  Google Scholar 

  31. 31

    Massalski, T. B. & Okamoto, H. Binary Alloy Phase Diagrams (ASM International, 1990).

    Google Scholar 

  32. 32

    Moon, G. D. et al. Assembled monolayers of hydrophilic particles on water surfaces. ACS Nano 5, 8600–8612 (2011).

    Article  Google Scholar 

  33. 33

    Stöber, W., Fink, A. & Bohn, E. Controlled growth of monodisperse silica spheres in the micron size range. J. Colloid Interface Sci. 26, 62–69 (1968).

    Article  Google Scholar 

  34. 34

    Frens, G. Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nature 241, 20–22 (1973).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Battery Materials Research (BMR) Program in the Office of Vehicle Technologies of the US Department of Energy. H.-W.L. was supported by Basic Science Research Program through the National Research Foundation of Korea under Contract No. NRF-2012R1A6A3A03038593.

Author information

Affiliations

Authors

Contributions

K.Y. and Y.C. conceived the idea. K.Y., F.X. and P.-C.H. conducted the film deposition. K.Y. and Z.L. synthesized hollow spheres. K.Y. carried out the electrochemical tests. H.-W.L., Y.L. and Z.L. performed TEM characterizations. K.Y., P.-C.H., J.Z. and Z.L. worked on other characterizations. Y.C. and S.C. supervised the project and participated in the planning of research. K.Y., S.C. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Yi Cui.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–7, Supplementary Reference. (PDF 4730 kb)

Supplementary Video 1

In-situ lithium melting. Two examples of in situ melting of lithium metal particles encapsuled inside a nanocapsule, after electrochemical deposition. Nanocapsules with a single gold nanoparticle enclosed were used for clarity. (MOV 11831 kb)

Supplementary Video 2

In-situ lithium filling into nanocapsules. Lithium deposition inside nanocapsules is revealed by in situ transmission electron microscopy. The set-up was biased at a constant potential. Because the resistance of the cell decreased as lithium was gradually injected into the carbon structure, the lithiation/lithium-plating speed accelerated during the test. The playback speed changed at the point when lithium started to plate, to compensate the actual speed change. (MOV 12509 kb)

Supplementary Video 3

In-situ lithium cycling in nanocapsules. In situ observation of lithium cycling inside a nanocapsule. Carbon shells with single gold nanoparticles were used here for clarity, although tiny gold nanoparticles still exist on the inner wall of the carbon shell, which altered the nucleation of lithium at the first cycle. The gold nanoparticle was able to dissolve in lithium metal completely due to e-beam heating. Precipitation of gold was confined within the identical carbon shell, although the exact position may be random. (MOV 21885 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yan, K., Lu, Z., Lee, HW. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat Energy 1, 16010 (2016). https://doi.org/10.1038/nenergy.2016.10

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing