Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Dynamic spatial progression of isolated lithium during battery operations

Abstract

The increasing demand for next-generation energy storage systems necessitates the development of high-performance lithium batteries1,2,3. Unfortunately, current Li anodes exhibit rapid capacity decay and a short cycle life4,5,6, owing to the continuous generation of solid electrolyte interface7,8 and isolated Li (i-Li)9,10,11. The formation of i-Li during the nonuniform dissolution of Li dendrites12 leads to a substantial capacity loss in lithium batteries under most testing conditions13. Because i-Li loses electrical connection with the current collector, it has been considered electrochemically inactive or ‘dead’ in batteries14,15. Contradicting this commonly accepted presumption, here we show that i-Li is highly responsive to battery operations, owing to its dynamic polarization to the electric field in the electrolyte. Simultaneous Li deposition and dissolution occurs on two ends of the i-Li, leading to its spatial progression toward the cathode (anode) during charge (discharge). Revealed by our simulation results, the progression rate of i-Li is mainly affected by its length, orientation and the applied current density. Moreover, we successfully demonstrate the recovery of i-Li in Cu–Li cells with >100% Coulombic efficiency and realize LiNi0.5Mn0.3Co0.2O2 (NMC)–Li full cells with extended cycle life.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Dynamic polarization of i-Li under an electric field.
Fig. 2: Morphological evolution of the i-Li island.
Fig. 3: Quantification of the overpotentials on i-Li in coin cells.
Fig. 4: Progression and recovery of i-Li in coin cells during discharge.

Data availability

All the data that support the findings of this study are available from the corresponding author upon request. Source data are provided with this paper.

References

  1. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012); erratum Nat. Mater. 11, 172 (2012).

    CAS  Article  ADS  Google Scholar 

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

    CAS  Article  ADS  Google Scholar 

  3. Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2018).

    CAS  Article  ADS  Google Scholar 

  4. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    CAS  Article  ADS  Google Scholar 

  5. Cheng, X.-B., Zhang, R., Zhao, C.-Z. & Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).

    CAS  Article  Google Scholar 

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

    CAS  Article  Google Scholar 

  7. Lu, D. et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).

    Article  Google Scholar 

  8. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019)

    CAS  Article  ADS  Google Scholar 

  9. Yoshimatsu, I., Hirai, T. & Yamaki, J.-i. Lithium electrode morphology during cycling in lithium cells. J. Electrochem. Soc. 135, 2422–2427 (1988).

    CAS  Article  ADS  Google Scholar 

  10. Sanchez, A. J. et al. Plan-view operando video microscopy of Li metal anodes: identifying the coupled relationships among nucleation, morphology, and reversibility. ACS Energy Lett. 5, 994–1004 (2020).

    CAS  Article  Google Scholar 

  11. Gunnarsdóttir, A. B., Amanchukwu, C. V., Menkin, S. & Grey, C. P. Noninvasive in situ NMR study of “dead lithium” formation and lithium corrosion in full-cell lithium metal batteries. J. Am. Chem. Soc. 142, 20814–20827 (2020).

    Article  Google Scholar 

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

    CAS  Article  Google Scholar 

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

    CAS  Article  ADS  Google Scholar 

  14. Chen, K.-H. et al. Dead lithium: mass transport effects on voltage, capacity, and failure of lithium metal anodes. J. Mater. Chem. A 5, 11671–11681 (2017).

    CAS  Article  Google Scholar 

  15. Xu, S., Chen, K.-H., Dasgupta, N. P., Siegel, J. B. & Stefanopoulou, A. G. Evolution of dead lithium growth in lithium metal batteries: experimentally validated model of the apparent capacity loss. J. Electrochem. Soc. 166, A3456–A3463 (2019).

    CAS  Article  Google Scholar 

  16. Jin, C. et al. Rejuvenating dead lithium supply in lithium metal anodes by iodine redox. Nat. Energy 6, 378–387 (2021).

    CAS  Article  ADS  Google Scholar 

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

    CAS  Article  ADS  Google Scholar 

  18. 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).

    CAS  Article  ADS  Google Scholar 

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

    CAS  Article  ADS  Google Scholar 

  20. Weng, Y.-T. et al. An ultrathin ionomer interphase for high-efficiency lithium anode in carbonate-based electrolyte. Nat. Commun. 10, 5824 (2019).

    CAS  Article  ADS  Google Scholar 

  21. Lin, D. et al. Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent freon. Nano Lett. 17, 3731–3737 (2017).

    CAS  Article  ADS  Google Scholar 

  22. 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).

    CAS  Article  ADS  Google Scholar 

  23. Lin, D. et al. Three-dimensional stable lithium metal anode with nanoscale lithium islands embedded in ionically conductive solid matrix. Proc. Natl Acad. Sci. USA 114, 4613–4618 (2017).

    CAS  Article  Google Scholar 

  24. Chen, H. et al. Tortuosity effects in lithium-metal host anodes. Joule 4, 938–952 (2020).

    CAS  Article  Google Scholar 

  25. Mao, C., Ruther, R. E., Li, J., Du, Z. & Belharouak, I. Identifying the limiting electrode in lithium ion batteries for extreme fast charging. Electrochem. Commun. 97, 37–41 (2018).

    CAS  Article  Google Scholar 

  26. Belov, D. & Yang, M.-H. Investigation of the kinetic mechanism in overcharge process for Li-ion battery. Solid State Ionics 179, 1816–1821 (2008).

    CAS  Article  Google Scholar 

  27. Doyle, M., Fuller, T. F. & Newman, J. Modeling of galvanostatic charge and discharge of the lithium/polymer/insertion cell. J. Electrochem. Soc. 140, 1526–1533 (1993).

    CAS  Article  ADS  Google Scholar 

  28. Fuller, T. F., Doyle, M. & Newman, J. Simulation and optimization of the dual lithium ion insertion cell. J. Electrochem. Soc. 141, 1–10 (1994).

    CAS  Article  ADS  Google Scholar 

  29. Zheng, J. et al. Highly stable operation of lithium metal batteries enabled by the formation of a transient high-concentration electrolyte layer. Adv. Energy Mater. 6, 1502151 (2016).

    Article  ADS  Google Scholar 

Download references

Acknowledgements

Y.C. acknowledges 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), Battery 500 Consortium, and the eXtreme Fast Charge Cell Evaluation of Li-ion batteries (XCEL) programmes.

Author information

Authors and Affiliations

Authors

Contributions

F.L. and Y.C. conceived the idea and designed the experiments. F.L. conducted the electrochemical characterizations. R.X. conducted numerical simulations. Y.W. and A.Y. helped with the optical-cell fabrication. J.X. and Y.Z. designed and customized the multi-electrode cells. Z.Y. and H.C. prepared the electrolyte. Z.Z. performed SEM characterizations. D.T.B., Y.Y., W.H., H.W. and X.X. helped with the cell fabrication and electrochemical characterizations. F.L. 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 interests.

Additional information

Peer review information Nature thanks Peng Bai and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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

Extended data figures and tables

Extended Data Fig. 1 Configuration of optical cells with i-Li island between electrodes.

a, Experimental setup. b, Optical image of the deposited lithium on the Cu island. The scale bar is 100 µm.

Extended Data Fig. 2 Compositional evolution on i-Li island during charge.

a, b, X-ray photoelectron spectroscopy analysis of the ends of i-Li island near Li anode (a) and NMC cathode (b) after 3 h charging.

Source data

Extended Data Fig. 3 Morphological evolution of ‘dead Li’ during charge.

Optical images showing the evolution process of micrometre-sized, electrochemically generated ‘dead Li’ filaments under a charging current of 20 µA. The scale bar is 20 µm.

Extended Data Fig. 4 Potential distributions in the electrolyte during battery operations.

a, b, The potential distribution in the electrolyte during charge (a) and discharge (b). The direction of Li+ flux is shown in black arrows. The initial and end states are at t = 100 s and 2 h, respectively.

Extended Data Fig. 5 The dynamic response and spatial progression of i-Li during battery operations.

a, b, The absolute overpotentials at two ends of i-Li with different width (a) and length (b) during charge. c, The maximum current densities at the ends of i-Li filaments and Li electrode under various current densities during discharge. d, The migration distance of i-Li with different orientations at the end of 1C discharge (1C = 3 mA cm−2). The orientation of i-Li is defined as the angle between i-Li and the electric field. 0° and 90° represent the directions along and perpendicular to the electric field, respectively.

Source data

Extended Data Fig. 6 Progression of i-Li in coin cells during discharge.

a, Voltage–capacity profiles of NMC–G cells with different cell configurations. NMC–polyimide (PI)–G cells with/without Cu present identical voltage profiles, indicating that the addition of Cu does not influence the electrochemical performance of NMC–G cell. Red arrow marks the voltage fluctuation observed in NMC–PI–G cell with Cu/Li due to i-Li’s progression. Meanwhile, the NMC–polypropylene–G cell with i-Li (Cu/Li) exhibits a smooth voltage profile, suggesting that i-Li could not penetrate through the nano-sized pores of commercial polypropylene (PP) separators. b, c, SEM images of Cu/Li (bottom) and polyimide membrane (top) after 5-min (b) and 1-h charge (c), showing that i-Li penetrates through the polyimide membrane. Arrows point out the Li dendrites on the edge of polyimide membrane. The scale bars are 10 µm.

Source data

Extended Data Fig. 7 The recovery of ‘dead Li;’ during discharge.

a, A representative voltage profile of Cu–Li cell during i-Li formation cycle. b, Capacity of ‘dead Li’ on average. Each coloured sphere represents the CE of one Cu–Li cell, the box shows the average CE of ten cells, and the error bar illustrates 1 standard deviation. c, The recovery percentage of ‘dead Li’ under different stripping currents.

Source data

Extended Data Fig. 8 Coulombic efficiency measurements of Cu–Li half-cells with/without activation in the presence of ‘dead Li’.

ad, The stripping conditions are 0.5 mA cm−2 with an activation step of a, none, b, 3 mA cm−2 for 1 min, c, 3 mA cm−2 for 2 mins, and d, 6 mA cm−2 for 1 min. For the average CE measurement, a standard protocol is followed: (1) 5 mAh cm−2 of Li is deposited onto Cu under 0.5 mA cm−2 as a Li reservoir, (2) repeatedly deposit 1 mAh cm−2 of Li (0.5 mA cm−2) and strip under different conditions for ten cycles, (3) strip all active Li (0.5 mA cm−2) until 1 V. Accumulated ‘dead Li’ are formed by 5 cycles of Li deposition (3 mA cm−2, 1  h) and stripping (0.5 mA cm−2 until 1 V).

Source data

Extended Data Fig. 9 Electrochemical performance of NMC–Li cells with/without activation.

a, Coulombic efficiency and b, cycle life of NMC–Li cells (150%-excessed Li) with/without activation. c, Specific capacity and d, cycle life of NMC–Li cells (300%-excessed Li) under a fast-charging condition. Each coloured sphere represents the cycle life of one NMC–Li cell, the box shows the average cycle life of three cells, and the error bar illustrates 1 standard deviation. Cycle life is defined as the cycle number when the cell capacity falls below 80% of its initial capacity. TF stands for temperature fluctuation.

Source data

Extended Data Table 1 Parameters used in the numerical modelling

Source data

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Liu, F., Xu, R., Wu, Y. et al. Dynamic spatial progression of isolated lithium during battery operations. Nature 600, 659–663 (2021). https://doi.org/10.1038/s41586-021-04168-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-021-04168-w

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

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