Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Abstract

Stable operation of rechargeable lithium-based batteries at low temperatures is important for cold-climate applications, but is plagued by dendritic Li plating and unstable solid–electrolyte interphase (SEI). Here, we report on high-performance Li metal batteries under low-temperature and high-rate-charging conditions. The high performance is achieved by using a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of the SEI and deposition morphology of Li metal anodes. A multilayer SEI that contains a lithium fluoride-rich inner phase and amorphous outer layer effectively seals the Li surface, in contrast to the conventional SEI, which is non-passive at low temperatures. Consequently, galvanic Li corrosion and self-discharge are suppressed, stable Li deposition is achieved from −60 °C to 45 °C, and a Li | LiCoO2 cell with a capacity of 2.0 mAh cm−2 displays a 200-cycle life at −15 °C with a recharge time of 45 min.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: A stable low-temperature SEI regulated by an EAM on Cu.
Fig. 2: In situ decomposition of the EAM during SEI formation.
Fig. 3: Li nucleation and growth regulated by the EAM Cu.
Fig. 4: SEI nanostructure regulated by the EAM.
Fig. 5: EAM decomposition at the interface by nanoscale depth-profiling XPS.
Fig. 6: Composition of Li metal anode SEI formed at 25° and −15 °C.
Fig. 7: Battery performance under low-temperature conditions.
Fig. 8: Low-temperature SEI chemistry studied by modelling and quantitative NMR.

Data availability

All relevant data are included in the paper and its Supplementary Information.

References

  1. 1.

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

    Google Scholar 

  2. 2.

    Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

    Google Scholar 

  3. 3.

    Nagasubramanian, G. Electrical characteristics of 18650 Li-ion cells at low temperatures. J. Appl. Electrochem. 31, 99–104 (2001).

    Google Scholar 

  4. 4.

    Zhang, S. S., Xu, K. & Jow, T. R. The low temperature performance of Li-ion batteries. J. Power Sources 115, 137–140 (2003).

    Google Scholar 

  5. 5.

    Lin, H.-p et al. Low-temperature behavior of Li-ion cells. Electrochem. Solid-State Lett. 4, A71 (2002).

    Google Scholar 

  6. 6.

    Petzl, M., Kasper, M. & Danzer, M. A. Lithium plating in a commercial lithium-ion battery – a low-temperature aging study. J. Power Sources 275, 799–807 (2015).

    Google Scholar 

  7. 7.

    Fleischhammer, M., Waldmann, T., Bisle, G., Hogg, B. -I. & Wohlfahrt-Mehrens, M. Interaction of cyclic ageing at high-rate and low temperatures and safety in lithium-ion batteries. J. Power Sources 274, 432–439 (2015).

    Google Scholar 

  8. 8.

    Ratnakumar, B. V. et al. Lithium ion batteries for Mars exploration missions. Electrochim. Acta 45, 1513–1517 (2000).

    Google Scholar 

  9. 9.

    Rodrigues, M.-T. F. et al. A materials perspective on Li-ion batteries at extreme temperatures. Nat. Energy 2, 17108 (2017).

    Google Scholar 

  10. 10.

    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).

    Google Scholar 

  11. 11.

    Peled, E. & Menkin, S. Review—SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).

    Google Scholar 

  12. 12.

    Scrosati, B. & Garche, J. Lithium batteries: Status, prospects and future. J. Power Sources 195, 2419–2430 (2010).

    Google Scholar 

  13. 13.

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

    Google Scholar 

  14. 14.

    Wang, C., Appleby, A. J. & Little, F. E. Low-temperature characterization of lithium-ion carbon anodes via microperturbation measurement. J. Electrochem. Soc. 149, A754 (2002).

    Google Scholar 

  15. 15.

    Zhang, S. S., Xu, K. & Jow, T. R. A new approach toward improved low temperature performance of Li-ion battery. Electrochem. Commun. 4, 928–932 (2002).

    Google Scholar 

  16. 16.

    Smart, M. C. et al. Improved performance of lithium-ion cells with the use of fluorinated carbonate-based electrolytes. J. Power Sources 119–121, 359–367 (2003).

    Google Scholar 

  17. 17.

    Smart, M. C. et al. Irreversible capacities of graphite in low-temperature electrolytes for lithium-ion batteries. J. Electrochem. Soc. 146, 3963 (1999).

    Google Scholar 

  18. 18.

    Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    Google Scholar 

  19. 19.

    Tung, S.-O., Ho, S., Yang, M., Zhang, R. & Kotov, N. A. A dendrite-suppressing composite ion conductor from aramid nanofibres. Nat. Commun. 6, 6152 (2015).

    Google Scholar 

  20. 20.

    Choudhury, S., Mangal, R., Agrawal, A. & Archer, L. A. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 6, 10101 (2015).

    Google Scholar 

  21. 21.

    Liu, K. et al. Lithium metal anodes with an adaptive “solid-liquid” interfacial protective layer. J. Am. Chem. Soc. 139, 4815–4820 (2017).

    Google Scholar 

  22. 22.

    Kim, M. S. et al. Langmuir–Blodgett artificial solid-electrolyte interphases for practical lithium metal batteries. Nat. Energy 3, 889–898 (2018).

    Google Scholar 

  23. 23.

    Gao, Y. et al. Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J. Am. Chem. Soc. 139, 15288–15291 (2017).

    Google Scholar 

  24. 24.

    Gao, Y. et al. Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Mater. 18, 384–389 (2019).

    Google Scholar 

  25. 25.

    Liang, X. et al. A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 6, 17119 (2017).

    Google Scholar 

  26. 26.

    Dudney, N. J. Addition of a thin-film inorganic solid electrolyte (Lipon) as a protective film in lithium batteries with a liquid electrolyte. J. Power Sources 89, 176–179 (2000).

    Google Scholar 

  27. 27.

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

    Google Scholar 

  28. 28.

    Basile, A., Bhatt, A. I. & O’Mullane, A. P. Stabilizing lithium metal using ionic liquids for long-lived batteries. Nat. Commun. 7, 11794 (2016).

    Google Scholar 

  29. 29.

    Zeng, Z. et al. Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries. Nat. Energy 3, 674–681 (2018).

    Google Scholar 

  30. 30.

    Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).

    Google Scholar 

  31. 31.

    Wei, S. et al. Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes. Sci. Adv. 4, eaao6243 (2018).

    Google Scholar 

  32. 32.

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

    Google Scholar 

  33. 33.

    Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 11, 626–632 (2016).

    Google Scholar 

  34. 34.

    Yang, C.-P., Yin, Y.-X., Zhang, S.-F., Li, N.-W. & Guo, Y.-G. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 6, 8058 (2015).

    Google Scholar 

  35. 35.

    Li, G. et al. Stable metal battery anodes enabled by polyethylenimine sponge hosts by way of electrokinetic effects. Nat. Energy 3, 1076–1083 (2018).

    Google Scholar 

  36. 36.

    Zhang, R. et al. Lithiophilic sites in doped graphene guide uniform lithium nucleation for dendrite-free lithium metal anodes. Angew. Chem. Int. Ed. 56, 7764–7768 (2017).

    Google Scholar 

  37. 37.

    Rustomji, C. S. et al. Liquefied gas electrolytes for electrochemical energy storage devices. Science 356, eaal4263 (2017).

    Google Scholar 

  38. 38.

    Yang, Y. et al. High-efficiency lithium-metal anode enabled by liquefied gas electrolytes. Joule 3, 1986–2000 (2019).

    Google Scholar 

  39. 39.

    Plichta, E. J. & Behl, W. K. A low-temperature electrolyte for lithium and lithium-ion batteries. J. Power Sources 88, 192–196 (2000).

    Google Scholar 

  40. 40.

    Uvdal, K., Bodö, P. & Liedberg, B. ʟ-cysteine adsorbed on gold and copper: An X-ray photoelectron spectroscopy study. J. Colloid Interface Sci. 149, 162–173 (1992).

    Google Scholar 

  41. 41.

    Caprioli, F., Decker, F., Marrani, A. G., Beccari, M. & Di Castro, V. Copper protection by self-assembled monolayers of aromatic thiols in alkaline solutions. Phys. Chem. Chem. Phys. 12, 9230–9238 (2010).

    Google Scholar 

  42. 42.

    Mandler, D. & Turyan, I. Applications of self-assembled monolayers in electroanalytical chemistry. Electroanalysis 8, 207–213 (1996).

    Google Scholar 

  43. 43.

    Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy. Science 358, 506–510 (2017).

    Google Scholar 

  44. 44.

    Wang, F. et al. Chemical distribution and bonding of lithium in intercalated graphite: Identification with optimized electron energy loss spectroscopy. ACS Nano 5, 1190–1197 (2011).

    Google Scholar 

  45. 45.

    Chen, S. et al. Functional organosulfide electrolyte promotes an alternate reaction pathway to achieve high performance in lithium-sulfur batteries. Angew. Chem. Int. Ed. 55, 4231–4235 (2016).

    Google Scholar 

  46. 46.

    Ding, F. et al. Effects of carbonate solvents and lithium salts on morphology and coulombic efficiency of lithium electrode. J. Electrochem. Soc. 160, A1894–A1901 (2013).

    Google Scholar 

  47. 47.

    Lin, D. et al. Fast galvanic lithium corrosion involving a Kirkendall-type mechanism. Nat. Chem. 11, 382–389 (2019).

    Google Scholar 

  48. 48.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Google Scholar 

  49. 49.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Google Scholar 

  50. 50.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Google Scholar 

  51. 51.

    Hoover, W. G. Canonical dynamics: equilibrium phase-space distributions. Phys. Rev. A 31, 1695–1697 (1985).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award no. DE-EE0008198. T.R. and A.T.N. acknowledge the provision of computing resources on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. We thank S. Zheng for discussion on the performance of batteries at low temperatures.

Author information

Affiliations

Authors

Contributions

Y.G. and Donghai Wang conceived and designed the experiments. Y.G., T.C., and S.L. prepared the materials and electrodes. T.R. and A.T.N. designed and conducted the electrochemical simulation of the low-temperature SEI. K.W. and H.W. performed the TEM experiments. Y.G. and Daiwei Wang conducted the electrochemical tests. All authors discussed and analysed the data. Y.G. and Donghai Wang prepared the manuscript with input from all co-authors.

Corresponding author

Correspondence to Donghai Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary information

Supplementary Figs. 1–51, discussion, Tables 1–9 and refs. 1–7.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Gao, Y., Rojas, T., Wang, K. et al. Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface. Nat Energy 5, 534–542 (2020). https://doi.org/10.1038/s41560-020-0640-7

Download citation

Further reading

Search

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