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Corrosion of lithium metal anodes during calendar ageing and its microscopic origins

Abstract

Rechargeable lithium (Li) metal batteries must have long cycle life and calendar life (retention of capacity during storage at open circuit). Particular emphasis has been placed on prolonging the cycle life of Li metal anodes, but calendar ageing is less understood. Here, we show that Li metal loses at least 2–3% of its capacity after only 24 hours of ageing, regardless of the electrolyte chemistry. These losses of capacity during calendar ageing also shorten the cycle life of Li metal batteries. Cryogenic transmission electron microscopy shows that chemical corrosion of Li and the continuous growth of the solid electrolyte interphase—a passivation film on Li—cause the loss of capacity. Electrolytes with long cycle life do not necessarily form a solid electrolyte interphase with more resistance to chemical corrosion, so functional electrolytes must simultaneously minimize the rate of solid electrolyte interphase growth and the surface area of electrodeposited Li metal.

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Fig. 1: Effect of resting intervals on the CE of lithium metal anodes.
Fig. 2: Cryo-(S)TEM mapping of SEI growth on Li metal during calendar ageing in both low- and high-performance electrolytes.
Fig. 3: Time-dependent interfacial resistance and microstructure of electrodeposited Li metal in select electrolytes.
Fig. 4: Effect of calendar ageing on the cycle life of anode-free full-cells. The full-cells use the LiBF4/LiDFOB (FEC:DEC) electrolyte and a LFP cathode (2 mA h cm–2 loading, cycling at C/2, 1 mA cm–2).
Fig. 5: Schematic of the relationship between the rate of SEI growth, surface area (SA) of Li and capacity loss of Li metal anodes in liquid electrolytes.

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Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information file.

References

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  3. Fang, C., Wang, X. & Meng, Y. S. Key issues hindering a practical lithium-metal anode. Trends Chem. 1, 152–158 (2019).

    Article  Google Scholar 

  4. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).

    Article  Google Scholar 

  5. Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).

    Article  Google Scholar 

  6. Li, Y. et al. Correlating structure and function of battery interphases at atomic resolution using cryoelectron microscopy. Joule 2, 2167–2177 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  8. Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).

    Article  Google Scholar 

  9. 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).

    Article  Google Scholar 

  10. Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 4, 796–805 (2019).

    Article  Google Scholar 

  11. Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).

    Article  Google Scholar 

  12. Niu, C. et al. Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions. Nat. Nanotechnol. 14, 594–601 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

  14. Adams, B. D., Zheng, J., Ren, X., Xu, W. & Zhang, J. G. Accurate determination of Coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2017).

    Article  Google Scholar 

  15. Crozier, C., Apostolopoulou, D. & Mcculloch, M. Clustering of usage profiles for electric vehicle behaviour analysis. In 2018 IEEE PES Innovative Smart Grid Technologies Conference Europe (ISGT-Europe) 1–6 (IEEE, 2018).

  16. Speidel, S. & Bräunl, T. Driving and charging patterns of electric vehicles for energy usage. Renew. Sustain. Energy Rev. 40, 97–110 (2014).

    Article  Google Scholar 

  17. Kolesnikov, A. et al. Galvanic corrosion of lithium-powder-based electrodes. Adv. Energy Mater. 10, 2000017 (2020).

    Article  Google Scholar 

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

    Article  Google Scholar 

  19. Keil, P. et al. Calendar aging of lithium-ion batteries I. Impact of the graphite anode on capacity fade. J. Electrochem. Soc. 163, A1872–A1880 (2016).

    Article  Google Scholar 

  20. Dubarry, M., Qin, N. & Brooker, P. Calendar aging of commercial Li-ion cells of different chemistries – a review. Curr. Opin. Electrochem. 9, 106–113 (2018).

    Article  Google Scholar 

  21. Attia, P. M., Das, S., Harris, S. J., Bazant, M. Z. & Chueh, W. C. Electrochemical kinetics of SEI growth on carbon black: part I. Experiments. J. Electrochem. Soc. 166, 97–106 (2019).

    Article  Google Scholar 

  22. Moretti, A. et al. A comparison of formation methods for graphite//LiFePO4 cells. Batter. Supercaps 2, 240–247 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

  24. Yu, Z. et al. Molecular design of electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Article  Google Scholar 

  25. Liu, Y. et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode. Nat. Commun. 9, 3656 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  27. Genovese, M. et al. Hot formation for improved low temperature cycling of anode-free lithium metal batteries. J. Electrochem. Soc. 166, A3342–A3347 (2019).

    Article  Google Scholar 

  28. Wang, J. et al. Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy. Nat. Energy 4, 664–670 (2019).

    Article  Google Scholar 

  29. Wang, H. et al. Wrinkled graphene cages as hosts for high-capacity Li metal anodes shown by cryogenic electron microscopy. Nano Lett. 19, 1326–1335 (2019).

    Article  Google Scholar 

  30. Pei, A., Zheng, G., Shi, F., Li, Y. & Cui, Y. Nanoscale nucleation and growth of electrodeposited lithium metal. Nano Lett. 17, 1132–1139 (2017).

    Article  Google Scholar 

  31. Huang, W. et al. Evolution of the solid–electrolyte interphase on carbonaceous anodes visualized by atomic-resolution cryogenic electron microscopy. Nano Lett. 19, 5140–5148 (2019).

    Article  Google Scholar 

  32. Huang, W. et al. Dynamic structure and chemistry of the silicon solid-electrolyte interphase visualized by cryogenic electron microscopy. Matter 1, 1232–1245 (2019).

    Article  Google Scholar 

  33. Pinson, M. B. & Bazant, M. Z. Theory of SEI formation in rechargeable batteries: capacity fade, accelerated aging and lifetime prediction. J. Electrochem. Soc. 160, A243–A250 (2013).

    Article  Google Scholar 

  34. Zhou, Y. et al. Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery. Nat. Nanotechnol. 15, 224–230 (2020).

    Article  Google Scholar 

  35. Lu, P., Li, C., Schneider, E. W. & Harris, S. J. Chemistry, impedance, and morphology evolution in solid electrolyte interphase films during formation in lithium ion batteries. J. Phys. Chem. C 118, 896–903 (2014).

    Article  Google Scholar 

  36. Huang, W., Wang, H., Boyle, D. T., Li, Y. & Cui, Y. Resolving nanoscopic and mesoscopic heterogeneity of fluorinated species in battery solid-electrolyte interphases by cryogenic electron microscopy. ACS Energy Lett. 5, 1128–1135 (2020).

    Article  Google Scholar 

  37. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4417 (2004).

    Article  Google Scholar 

  38. Brown, Z. L., Jurng, S., Nguyen, C. C. & Lucht, B. L. Effect of fluoroethylene carbonate electrolytes on the nanostructure of the solid electrolyte interphase and performance of lithium metal anodes. ACS Appl. Energy Mater. 1, 26–31 (2018).

    Article  Google Scholar 

  39. Cody, G. D. et al. Quantitative organic and light‐element analysis of comet 81P/Wild 2 particles using C‐, N‐, and O‐μ‐XANES. Meteorit. Planet. Sci. 43, 353–365 (2008).

    Article  Google Scholar 

  40. le Guillou, C., Bernard, S., de la Pena, F. & le Brech, Y. XANES-based quantification of carbon functional group concentrations. Anal. Chem. 90, 8379–8386 (2018).

    Article  Google Scholar 

  41. Braun, A., Kubatova, A., Wirick, S. & Mun, S. B. Radiation damage from EELS and NEXAFS in diesel soot and diesel soot extracts. J. Electron Spectros. Relat. Phenom. 170, 42–48 (2009).

    Article  Google Scholar 

  42. Endo, E., Ata, M., Sekai, K. & Tanaka, K. Spin trapping study of gradual decomposition of electrolyte solutions for lithium secondary batteries. J. Electrochem. Soc. 146, 49–53 (1999).

    Article  Google Scholar 

  43. Gourdin, G., Collins, J., Zheng, D., Foster, M. & Qu, D. Spectroscopic compositional analysis of electrolyte during initial SEI layer formation. J. Phys. Chem. C 118, 17383–17394 (2014).

    Article  Google Scholar 

  44. Soto, F. A. et al. Formation and growth mechanisms of solid-electrolyte interphase layers in rechargeable batteries. Chem. Mater. 27, 7990–8000 (2015).

    Article  Google Scholar 

  45. Huang, W. et al. Nanostructural and electrochemical evolution of the solid-electrolyte interphase on CuO nanowires revealed by cryogenic electron microscopy and impedance spectroscopy. ACS Nano 13, 737–744 (2019).

    Article  Google Scholar 

  46. Boyle, D. T. et al. Transient voltammetry with ultramicroelectrodes reveals the electron transfer kinetics of lithium metal anodes. ACS Energy Lett. 5, 701–709 (2020).

    Article  Google Scholar 

  47. Wood, S. M. et al. Predicting calendar aging in lithium metal secondary batteries: the impacts of solid electrolyte interphase composition and stability. Adv. Energy Mater. 8, 1801427 (2018).

    Article  Google Scholar 

  48. Attia, P. M., Cheuh, W. C. & Harris, S. J. Revisiting the t0.5 dependence of SEI growth. J. Electrochem. Soc. 167, 090535 (2020).

    Article  Google Scholar 

  49. Aurbach, D. & Zaban, J. Impedance spectroscopy of lithium electrodes: part 1. General behavior in propylene carbonate solutions and the correlation to surface chemistry and cycling efficiency. J. Electroanal. Chem. 348, 155–179 (1993).

    Article  Google Scholar 

  50. Aurbach, D. & Zaban, J. Impedance spectroscopy of lithium electrodes: part 2. The behaviour in propylene carbonate solutions — the significance of the data obtained. J. Electroanal. Chem. 367, 15–25 (1994).

    Article  Google Scholar 

  51. Aurbach, D. & Zaban, J. Impedance spectroscopy of lithium electrodes: part 3. The importance of Li electrode preparation. J. Electroanal. Chem. 365, 41–45 (1994).

    Article  Google Scholar 

  52. Zhuo, Z. et al. Breathing and oscillating growth of solid-electrolyte-interphase upon electrochemical cycling. Chem. Commun. 54, 814–817 (2018).

    Article  Google Scholar 

  53. Zheng, J. et al. Physical orphaning versus chemical Instability: is dendritic electrodeposition of Li fatal? ACS Energy Lett. 4, 1349–1355 (2019).

    Article  Google Scholar 

  54. Harlow, J. E. et al. A wide range of testing on an excellent lithium-ion cell chemistry to be used as benchmarks for new battery technologies. J. Electrochem. Soc. 166, A3031–A3044 (2019).

    Article  Google Scholar 

  55. Zaban, A., Zinigrad, E. & Aurbach, D. Impedance spectroscopy of lithium electrodes. 4. A general simple model of the Li–solution interphase in polar aprotic systems. J. Phys. Chem. 100, 3089–3101 (1996).

    Article  Google Scholar 

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Acknowledgements

We acknowledge 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 and Battery 500 Consortium. The cryo-TEM research is supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under contract DE-AC02-76SF00515. D.T.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program. Scanning electron microscopy and TEM were performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. The K3 IS camera and support are courtesy of Gatan. We also acknowledge H. Wang for help designing the schematic in Fig. 5.

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D.T.B. and Y.C. conceived the idea. D.T.B. designed the research with guidance from Y.C., carried out the electrochemical measurements and analysed the data. W.H. and Y.L. helped design the cryo-(S)TEM experiments, and W.H. carried out the cryo-(S)TEM experiments and analysed the data. W.Z. carried out the cryo-TEM selected area electron diffraction (SAED) and additional EELS measurements. H.W. and H.C. helped carry out and interpret the XPS experiments and synthesized host materials. H.C. helped with scanning electron microscopy. Z.Y. synthesized electrolyte materials. D.T.B., W.H. and Y.C. wrote the manuscript.

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Correspondence to Yi Cui.

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Peer review information Nature Energy thanks Marian Stan, Yifei Yuan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–21, Tables 1–2 and references.

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Boyle, D.T., Huang, W., Wang, H. et al. Corrosion of lithium metal anodes during calendar ageing and its microscopic origins. Nat Energy 6, 487–494 (2021). https://doi.org/10.1038/s41560-021-00787-9

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