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
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
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
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).
Xiao, J. How lithium dendrites form in liquid batteries. Science 366, 426–427 (2019).
Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).
Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).
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).
Lu, D. et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).
Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).
Niu, C. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nat. Energy 6, 723–732 (2021).
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).
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).
Zhang, N. & Tang, H. Dissecting anode swelling in commercial lithium-ion batteries. J. Power Sources 218, 52–55 (2012).
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).
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).
Blazek, P. et al. Axially and radially inhomogeneous swelling in commercial 18650 Li-ion battery cells. J. Energy Storage 52, 104563 (2022).
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).
Taylor, N. Cell electrode pressure. Battery Design https://www.batterydesign.net/cell-electrode-pressure/ (2023).
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).
Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat. Energy 5, 693–702 (2020).
Fang, C. et al. Pressure-tailored lithium deposition and dissolution in lithium metal batteries. Nat. Energy 6, 987–994 (2021).
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).
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).
Kim, S. et al. Correlation of electrochemical and mechanical responses: differential analysis of rechargeable lithium metal cells. J. Power Sources 463, 228180 (2020).
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).
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).
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).
Wu, B. et al. Good practices for rechargeable lithium metal batteries. J. Electrochem. Soc. 166, A4141 (2019).
Gao, X. et al. Solid-state lithium battery cathodes operating at low pressures. Joule 6, 636–646 (2022).
Ye, L. & Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 593, 218–222 (2021).
Zahiri, B. et al. Revealing the role of the cathode–electrolyte interface on solid-state batteries. Nat. Mater. 20, 1392–1400 (2021).
Yuan, X., Liu, B., Mecklenburg, M. & Li, Y. Ultrafast deposition of faceted lithium polyhedra by outpacing SEI formation. Nature 620, 86–91 (2023).
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).
McNulty, R. C. et al. Understanding the limits of Li-NMC811 half-cells. J. Mater. Chem. A 11, 18302–18312 (2023).
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).
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).
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).
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).
Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).
Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).
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).
Doll, K., Harrison, N. M. & Saunders, V. R. A density functional study of lithium bulk and surfaces. J. Phys. Condens. Matter 11, 5007 (1999).
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
Authors and Affiliations
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
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.
About this article
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
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41560-024-01488-9