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Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries

Abstract

The rechargeable lithium metal battery has attracted wide attention as a next-generation energy storage technology. However, simultaneously achieving high cell-level energy density and long cycle life in realistic batteries is still a great challenge. Here we investigate the degradation mechanisms of Li || LiNi0.6Mn0.2Co0.2O2 pouch cells and present fundamental linkages among Li thickness, electrolyte depletion and the structure evolution of solid–electrolyte interphase layers. Different cell failure processes are discovered when tuning the anode to cathode capacity ratio in compatible electrolytes. An optimal anode to cathode capacity ratio of 1:1 emerges because it balances well the rates of Li consumption, electrolyte depletion and solid–electrolyte interphase construction, thus decelerating the increase of cell polarization and extending cycle life. Contrary to conventional wisdom, long cycle life is observed by using ultra-thin Li (20 µm) in balanced cells. A prototype 350 Wh kg−1 pouch cell (2.0 Ah) achieves over 600 long stable cycles with 76% capacity retention without a sudden cell death.

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Fig. 1: Four types of 350 Wh kg−1 pouch cells.
Fig. 2: Electrochemical performances of four types of 350 Wh kg1 Li || NMC622 pouch cells at 2.0 Ah level.
Fig. 3: Characterizations of the NMC622 electrodes after long cycling in 350 Wh kg−1 pouch cells.
Fig. 4: Postmortem characterizations of the Li metal anodes before and after cycling in four types of 350 Wh kg−1 pouch cell.
Fig. 5: Pouch cell thickness average swelling comparison after cycling.
Fig. 6: Schematic illustration of the degradation mechanisms and cell capacity fading models.

Data availability

All data generated this study are included in the published article and its Supplementary Information.

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Acknowledgements

This research was 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, 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-AC05-76RLO1830. We thank L. Zou and C. Wang of PNNL for the TEM characterizations. We thank K. Murata of Nippon Shokubai for providing the LiFSI salt.

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J.L. directed and led the research. J.X. led the pouch cell design and fabrication. C.N. assembled the pouch cells, performed the electrochemical measurements and carried out the characterizations. D.L., J.A.L. and C.S.A. participated in discussions. X.C., W.X. and J.-G.Z. provided the electrolyte. M.E.G. helped on cell disassembly and safety protection. M.S.W. provided advice for the research and for the analysis of the electrochemical results. C.N., J.X. and J.L. cowrote the manuscript with input from all authors.

Corresponding authors

Correspondence to Jie Xiao or Jun Liu.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Guohua Chen, Tetsuya Osaka and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–7.

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Niu, C., Liu, D., Lochala, J.A. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nat Energy 6, 723–732 (2021). https://doi.org/10.1038/s41560-021-00852-3

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  • DOI: https://doi.org/10.1038/s41560-021-00852-3

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