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.
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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.
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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.
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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.
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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.
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.
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.
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.
Extended Data Fig. 8 Coulombic efficiency measurements of Cu–Li half-cells with/without activation in the presence of ‘dead Li’.
a–d, 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).
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.
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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
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DOI: https://doi.org/10.1038/s41586-021-04168-w
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