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.

  • Article
  • Published:

Controlled large-area lithium deposition to reduce swelling of high-energy lithium metal pouch cells in liquid electrolytes

Nature Energy (2024)Cite this article

Subjects

Abstract

Lithium (Li) metal battery technology, renowned for its high energy density, faces practical challenges, particularly concerning large volume change and cell swelling. Despite the profound impact of external pressure on cell performance, there is a notable gap in research regarding the interplay between external pressure and the electroplating behaviours of Li+ in large-format pouch cells. Here we delve into the impact of externally applied pressure on electroplating and stripping of Li in 350 Wh kg−1 pouch cells. Employing a hybrid design, we monitor and quantify self-generated pressures, correlating them with observed charge–discharge processes. A two-stage cycling process is proposed, revealing controlled pouch cell swelling of less than 10%, comparable to state-of-the-art Li-ion batteries. The pressure distribution across the cell surface unveils a complex Li+ detour behaviour during electroplating, highlighting the need for innovative strategies to address uneven Li plating and enhance Li metal battery technology.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: In situ pressure monitoring of three 350 Wh kg−1 Li/NMC622 pouch cells (2Ah) tested under different initial external pressure.
Fig. 2: Different stages of Li utilization in a Li/NMC622 pouch cell.
Fig. 3: Li metal pouch cells before and after extensive cycling under different initial pressures.
Fig. 4: Mapping of pressure distribution on the surface of a prototype 350 Wh kg−1 Li/NMC622 pouch cell (2Ah) during cycling and correlation to lithium metal morphologies after cycling.
Fig. 5: Experimental and theoretical study of Li+ detour behaviour during the electroplating process.

Similar content being viewed by others

Data availability

All relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.

References

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

    Article  CAS  ADS  Google Scholar 

  2. Xiao, J. How lithium dendrites form in liquid batteries. Science 366, 426–427 (2019).

    Article  CAS  PubMed  ADS  Google Scholar 

  3. Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).

    Article  CAS  Google Scholar 

  4. Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).

    Article  CAS  Google Scholar 

  5. Wu, B., Lochala, J., Taverne, T. & Xiao, J. The interplay between solid electrolyte interface (SEI) and dendritic lithium growth. Nano Energy 40, 34–41 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  ADS  Google Scholar 

  8. Niu, C. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nat. Energy 6, 723–732 (2021).

    Article  CAS  ADS  Google Scholar 

  9. Chen, H. et al. Free-standing ultrathin lithium metal–graphene oxide host foils with controllable thickness for lithium batteries. Nat. Energy 6, 790–798 (2021).

    Article  CAS  ADS  Google Scholar 

  10. Zhang, X.-Q. et al. A sustainable solid electrolyte interphase for high-energy-density lithium metal batteries under practical conditions. Angew. Chem. Int. Ed. 59, 3252–3257 (2020).

    Article  CAS  Google Scholar 

  11. Zhang, N. & Tang, H. Dissecting anode swelling in commercial lithium-ion batteries. J. Power Sources 218, 52–55 (2012).

    Article  CAS  ADS  Google Scholar 

  12. Zhang, N., Tang, H., Zhang, L. & Trifonova, A. Asymmetric electrode for suppressing cell swelling in commercial lithium ion batteries. J. Electrochem. Soc. 162, A2152 (2015).

    Article  CAS  Google Scholar 

  13. Aufschläger, A. et al. High precision measurement of reversible swelling and electrochemical performance of flexibly compressed 5Ah NMC622/graphite lithium-ion pouch cells. J. Energy Storage 59, 106483 (2023).

    Article  Google Scholar 

  14. Blazek, P. et al. Axially and radially inhomogeneous swelling in commercial 18650 Li-ion battery cells. J. Energy Storage 52, 104563 (2022).

    Article  Google Scholar 

  15. Kalaikkanal, K., Gobinath, N. & Mohan, R. Influence of swelling on the safety aspects of electric vehicle batteries—short review. IOP Conf. Ser. Earth Environ. Sci. 1161, 012010 (2023).

    Article  Google Scholar 

  16. Taylor, N. Cell electrode pressure. Battery Design https://www.batterydesign.net/cell-electrode-pressure/ (2023).

  17. Louli, A. J. et al. Exploring the impact of mechanical pressure on the performance of anode-free lithium metal cells. J. Electrochem. Soc. 166, A1291 (2019).

    Article  CAS  Google Scholar 

  18. Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat. Energy 5, 693–702 (2020).

    Article  CAS  ADS  Google Scholar 

  19. Fang, C. et al. Pressure-tailored lithium deposition and dissolution in lithium metal batteries. Nat. Energy 6, 987–994 (2021).

    Article  CAS  ADS  Google Scholar 

  20. Kasse, R. M. et al. Combined effects of uniform applied pressure and electrolyte additives in lithium-metal batteries. ACS Appl. Energy Mater. 5, 8273–8281 (2022).

    Article  CAS  Google Scholar 

  21. Duan, X. et al. Revealing the intrinsic uneven electrochemical reactions of Li metal anode in Ah-level laminated pouch cells. Adv. Funct. Mater. 33, 2210669 (2023).

    Article  CAS  Google Scholar 

  22. Kim, S. et al. Correlation of electrochemical and mechanical responses: differential analysis of rechargeable lithium metal cells. J. Power Sources 463, 228180 (2020).

    Article  CAS  Google Scholar 

  23. Harrison, K. L. et al. Effects of applied interfacial pressure on Li-metal cycling performance and morphology in 4 M LiFSI in DME. ACS Appl. Mater. Interfaces 13, 31668–31679 (2021).

    Article  CAS  PubMed  Google Scholar 

  24. Genovese, M., Louli, A. J., Weber, R., Hames, S. & Dahn, J. R. Measuring the coulombic efficiency of lithium metal cycling in anode-free lithium metal batteries. J. Electrochem. Soc. 165, A3321 (2018).

    Article  CAS  Google Scholar 

  25. Wünsch, M., Kaufman, J. & Sauer, D. U. Investigation of the influence of different bracing of automotive pouch cells on cyclic liefetime and impedance spectra. J. Energy Storage 21, 149–155 (2019).

    Article  Google Scholar 

  26. Wu, B. et al. Good practices for rechargeable lithium metal batteries. J. Electrochem. Soc. 166, A4141 (2019).

    Article  CAS  Google Scholar 

  27. Gao, X. et al. Solid-state lithium battery cathodes operating at low pressures. Joule 6, 636–646 (2022).

    Article  CAS  Google Scholar 

  28. Ye, L. & Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 593, 218–222 (2021).

    Article  CAS  PubMed  ADS  Google Scholar 

  29. Zahiri, B. et al. Revealing the role of the cathode–electrolyte interface on solid-state batteries. Nat. Mater. 20, 1392–1400 (2021).

    Article  CAS  PubMed  ADS  Google Scholar 

  30. Yuan, X., Liu, B., Mecklenburg, M. & Li, Y. Ultrafast deposition of faceted lithium polyhedra by outpacing SEI formation. Nature 620, 86–91 (2023).

    Article  CAS  PubMed  ADS  Google Scholar 

  31. Müller, V. et al. Effects of mechanical compression on the aging and the expansion behavior of Si/C-Composite|NMC811 in different lithium-ion battery cell formats. J. Electrochem. Soc. 166, A3796 (2019).

    Article  Google Scholar 

  32. McNulty, R. C. et al. Understanding the limits of Li-NMC811 half-cells. J. Mater. Chem. A 11, 18302–18312 (2023).

    Article  CAS  Google Scholar 

  33. Kleiner, K. et al. On the origin of reversible and irreversible reactions in LiNixCo(1 − x)/2Mn(1 − x)/2O2. J. Electrochem. Soc. 168, 120533 (2021).

    Article  CAS  ADS  Google Scholar 

  34. Yamada, Y. et al. Unusual stability of acetonitrile-based superconcentrated electrolytes for fast-charging lithium-ion batteries. J. Am. Chem. Soc. 136, 5039–5046 (2014).

    Article  CAS  PubMed  Google Scholar 

  35. 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  CAS  ADS  Google Scholar 

  36. Jia, H. et al. Is nonflammability of electrolyte overrated in the overall safety performance of lithium ion batteries? A sobering revelation from a completely nonflammable electrolyte. Adv. Energy Mater. 13, 2203144 (2023).

    Article  CAS  Google Scholar 

  37. Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).

    Article  PubMed  Google Scholar 

  38. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    Article  CAS  ADS  Google Scholar 

  39. Hehre, W. J., Ditchfield, R. & Pople, J. A. Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules. J. Chem. Phys. 56, 2257–2261 (1972).

    Article  CAS  ADS  Google Scholar 

  40. Doll, K., Harrison, N. M. & Saunders, V. R. A density functional study of lithium bulk and surfaces. J. Phys. Condens. Matter 11, 5007 (1999).

    Article  CAS  ADS  Google Scholar 

Download references

Acknowledgements

This research has been supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) through the Advanced Battery Materials Research Program (Battery500 Consortium). The SEM and TEM were conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the DOE under contract DE-AC05-76RL01830. The authors thank Q. Zhao for performing the XPS measurements.

Author information

Author notes

  1. These authors contributed equally: Dianying Liu, Bingbin Wu.

Authors and Affiliations

  1. Pacific Northwest National Laboratory, Richland, WA, USA

    Dianying Liu, Bingbin Wu, Yaobin Xu, Jacob Ellis, Arthur Baranovskiy, Dongping Lu, Joshua Lochala, Cassidy Anderson, Kevin Baar, Jun Liu & Jie Xiao

  2. University of Wisconsin Milwaukee, Milwaukee, WI, USA

    Deyang Qu

  3. University of Washington, Seattle, WA, USA

    Jihui Yang, Jun Liu & Jie Xiao

  4. Texas A&M University, College Station, TX, USA

    Diego Galvez-Aranda, Katherine-Jaime Lopez, Perla B. Balbuena & Jorge M. Seminario

Authors
  1. Dianying Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bingbin Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yaobin Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jacob Ellis
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Arthur Baranovskiy
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dongping Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Joshua Lochala
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Cassidy Anderson
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Kevin Baar
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Deyang Qu
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jihui Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Diego Galvez-Aranda
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Katherine-Jaime Lopez
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Perla B. Balbuena
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Jorge M. Seminario
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Jun Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Jie Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.X. and Jun Liu proposed the research. Dianying Liu and B.W. designed experiments, performed the electrochemical measurements, characterized materials and analysed the data. Dianying Liu and B.W. contributed equally to this work. Y.X. performed the SEM and TEM. J.E, A.B. and Dianying Liu designed the pouch cell testing fixtures. Jun Liu, C.A. and K.B. helped to make the pouch cells. D.G.-A., K.-J.L., P.B.B. and J.M.S. performed the theoretical calculations. D.Q. and J.Y. contributed to the discussion and provided suggestions. J.X. and Jun Liu wrote the manuscript with input from all other co-authors.

Corresponding authors

Correspondence to Jun Liu or Jie Xiao.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Subrahmanyam Goriparti and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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. 1–21 and Table 1.

Supplementary Data

Supplementary Figs. 2c, 3, 5–7, 9–13, 18 and 19.

Source data

Source Data Fig. 1

Statistical source data.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, D., Wu, B., Xu, Y. et al. Controlled large-area lithium deposition to reduce swelling of high-energy lithium metal pouch cells in liquid electrolytes. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01488-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s41560-024-01488-9

Search

Advanced 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