Abstract
Unregulated lithium (Li) growth is the major cause of low Coulombic efficiency, short cycle life and safety hazards for rechargeable Li metal batteries. Strategies that aim to achieve large granular Li deposits have been extensively explored, and yet it remains a challenge to achieve the ideal Li deposits, which consist of large Li particles that are seamlessly packed on the electrode and can be reversibly deposited and stripped. Here we report a dense Li deposition (99.49% electrode density) with an ideal columnar structure that is achieved by controlling the uniaxial stack pressure during battery operation. Using multiscale characterization and simulation, we elucidate the critical role of stack pressure on Li nucleation, growth and dissolution processes and propose a Li-reservoir-testing protocol to maintain the ideal Li morphology during extended cycling. The precise manipulation of Li deposition and dissolution is a critical step to enable fast charging and a low-temperature operation for Li metal batteries.
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 the data generated in this study are included in the published article and its supplementary information. Source data are provided with this paper.
References
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).
Fang, C., Wang, X. & Meng, Y. S. Key issues hindering a practical lithium–metal anode. Trends Chem. 1, 152–158 (2019).
Winter, M., Barnett, B. & Xu, K. Before Li ion batteries. Chem. Rev. 118, 11433–11456 (2018).
Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).
Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).
Chazalviel, J. N. Electrochemical aspects of the generation of ramified metallic electrodeposits. Phys. Rev. A 42, 7355–7367 (1990).
Xiao, J. How lithium dendrites form in liquid batteries. Science 366, 426–427 (2019).
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).
Yang, Y. et al. High-efficiency lithium-metal anode enabled by liquefied gas electrolytes. Joule 3, 1986–2000 (2019).
Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 1706102, 1706102 (2018).
Niu, C. et al. Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions. Nat. Nanotechnol. 14, 594–601 (2019).
Cao, D. et al. 3D Printed high-performance lithium metal microbatteries enabled by nanocellulose. Adv. Mater. 31, 68–71 (2019).
Xu, R. et al. Artificial interphases for highly stable lithium metal anode. Matter 1, 317–344 (2019).
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).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).
Hirai, T. Influence of electrolyte on lithium cycling efficiency with pressurized electrode stack. J. Electrochem. Soc. 141, 611 (1994).
Brandt, K. & Stiles, J. A. R. Battery and methods of making the battery. US Patent 5114804-A (1985).
Wilkinson, D. P., Blom, H., Brandt, K. & Wainwright, D. Effects of physical constraints on Li cyclability. J. Power Sources 36, 517–527 (1991).
Yin, X. et al. Insights into morphological evolution and cycling behaviour of lithium metal anode under mechanical pressure. Nano Energy 50, 659–664 (2018).
Louli, A. J. et al. Exploring the impact of mechanical pressure on the performance of anode-free lithium metal cells. J. Electrochem. Soc. 166, 1291–1299 (2019).
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).
Zhang, X. et al. Rethinking how external pressure can suppress dendrites in lithium metal batteries. J. Electrochem. Soc. 166, 3639–3652 (2019).
Masias, A., Felten, N., Garcia-Mendez, R., Wolfenstine, J. & Sakamoto, J. Elastic, plastic, and creep mechanical properties of lithium metal. J. Mater. Sci. 54, 2585–2600 (2019).
Xu, C., Ahmad, Z., Aryanfar, A., Viswanathan, V. & Greer, J. R. Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes. Proc. Natl Acad. Sci. USA 114, 57–61 (2017).
Wang, Y., Dang, D., Xiao, X. & Cheng, Y. T. Structure and mechanical properties of electroplated mossy lithium: effects of current density and electrolyte. Energy Storage Mater. 26, 276–282 (2020).
Alvarado, J. et al. Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ. Sci. 12, 780–794 (2019).
Lee, H. et al. Electrode edge effects and the failure mechanism of lithium-metal batteries. ChemSusChem 11, 3821–3828 (2018).
Gaissmaier, D., Fantauzzi, D. & Jacob, T. First principles studies of self-diffusion processes on metallic lithium surfaces. J. Chem. Phys. 150, 41723 (2019).
Ghassemi, H., Au, M., Chen, N., Heiden, P. A. & Yassar, R. S. Real-time observation of lithium fibers growth inside a nanoscale lithium-ion battery. Appl. Phys. Lett. 99, 123113 (2011).
Zeng, Z. et al. Visualization of electrode–electrolyte interfaces in LiPF6/EC/DEC electrolyte for lithium ion batteries via in situ TEM. Nano Lett. 14, 1745–1750 (2014).
He, Y. et al. Origin of lithium whisker formation and growth under stress. Nat. Nanotechnol. 14, 1042–1047 (2019).
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).
Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat. Energy 5, 693–702 (2020).
Ponce, V., Galvez-Aranda, D. E. & Seminario, J. M. Analysis of a Li-ion nanobattery with graphite anode using molecular dynamics simulations. J. Phys. Chem. C 121, 12959–12971 (2017).
Xu, Z. & Buehler, M. J. Nanoengineering heat transfer performance at carbon nanotube interfaces. ACS Nano 3, 2767–2775 (2009).
Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).
Stukowski, A. Visualization and analysis of atomistic simulation data with OVITO—the Open Visualization Tool. Model. Simul. Mater. Sci. Eng. 18, 015012 (2010).
Acknowledgements
This work was supported by the Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) under contract DE-EE0007764. Cryo-FIB was performed at the San Diego Nanotechnology Infrastructure (SDNI), a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (grant ECCS-1542148). We acknowledge the UC Irvine Materials Research Institute (IMRI) for the use of the cryo-TEM, funded in part by the National Science Foundation Major Research Instrumentation Program under grant CHE-1338173. Idaho National Laboratory is operated by Battelle Energy Alliance under contract no. DE-AC07-05ID14517 for the US Department of Energy. The US Government retains and the publisher, by accepting the article for publication, acknowledges that the US Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US Government purposes. We thank J. K. Greene for the lithium surface coverage area data analysis, and Y. Lin for the simulation results discussion.
Author information
Authors and Affiliations
Contributions
C.F. and Y.S.M. conceived the ideas. C.F. designed the experiments. B. Lu implemented the electrochemical tests. B. Lu, C.F. and D.C. performed the cryo-FIB experiments. G.P. and B. Liaw performed the MD simulations. M.Z. collected the cryo-TEM data. C.F. conducted TEM data interpretation. S.C. and M. Cai conducted the pouch cell tests. M. Ceja prepared the electrolytes. J.-M.D. conducted the load-cell design and calibration. C.F. wrote the manuscript. All the authors discussed the results and commented on the manuscript. All the authors gave approval to the final version of the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature Energy thanks Venkatasubramanian Viswanathan 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.
Supplementary information
Supplementary Information
Supplementary Discussion, Figs. 1–17 and Table 1.
Supplementary Video 1
Cryo-FIB-SEM 3D reconstruction of deposited Li at 70 kPa, 2 mA cm−2 for 0.333 mAh cm−2.
Supplementary Video 2
Cryo-FIB-SEM 3D reconstruction of deposited Li at 350 kPa, 2 mA cm−2 for 0.333 mAh cm−2.
Source data
Source Data Fig. 1
Battery cycling data for each data point in Fig. 1b.
Rights and permissions
About this article
Cite this article
Fang, C., Lu, B., Pawar, G. et al. Pressure-tailored lithium deposition and dissolution in lithium metal batteries. Nat Energy 6, 987–994 (2021). https://doi.org/10.1038/s41560-021-00917-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41560-021-00917-3
This article is cited by
-
Controlled large-area lithium deposition to reduce swelling of high-energy lithium metal pouch cells in liquid electrolytes
Nature Energy (2024)
-
External-pressure–electrochemistry coupling in solid-state lithium metal batteries
Nature Reviews Materials (2024)
-
Recovery of isolated lithium through discharged state calendar ageing
Nature (2024)
-
Cation replacement method enables high-performance electrolytes for multivalent metal batteries
Nature Energy (2024)
-
Regulating electrochemical performances of lithium battery by external physical field
Rare Metals (2024)