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Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis

Abstract

Anode-free lithium metal cells store 60% more energy per volume than conventional lithium-ion cells. Such high energy density can increase the range of electric vehicles by approximately 280 km or even enable electrified urban aviation. However, these cells tend to experience rapid capacity loss and short cycle life. Furthermore, safety issues concerning metallic lithium often remain unaddressed in the literature. Recently, we demonstrated long-lifetime anode-free cells using a dual-salt carbonate electrolyte. Here we characterize the degradation of anode-free cells with this lean (2.6 g Ah−1) liquid electrolyte. We observe deterioration of the pristine lithium morphology using scanning electron microscopy and X-ray tomography, and diagnose the cause as electrolyte degradation and depletion using nuclear magnetic resonance spectroscopy and ultrasonic transmission mapping. For the safety characterization tests, we measure the cell temperature during nail penetration. Finally, we use the insights gained in this work to develop an optimized electrolyte, extending the lifetime of anode-free cells to 200 cycles.

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Fig. 1: Comparison of anode-free and lithium-ion cells.
Fig. 2: Energy retention and lithium morphology.
Fig. 3: Electrochemical and electrolyte analysis.
Fig. 4: Evolution of lithium morphology.
Fig. 5: The impact of increasing porosity.
Fig. 6: Safety characterization.
Fig. 7: High-concentration dual-salt electrolyte.

Data availability

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

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Acknowledgements

This research was financially supported by Tesla Canada and NSERC under the Industrial Research Chairs Program. A.J.L. and A.E. thank NSERC, the Killam Foundation and the Nova Scotia Graduate Scholarship programmes for financial support. M.G. thanks the NSERC PDF Program. We acknowledge J. Li (formerly of BASF) and D. J. Xiong (formerly of Capchem) for providing the chemicals used in the electrolytes. We also acknowledge P. Scallion for SEM support, as well as S. Trussler for expert fabrication of the parts used in this work.

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Contributions

A.J.L., M.G., R.W. and J.R.D. conceived the idea. A.J.L. performed the electrochemical measurements and the SEM analysis with the assistance of M.C. and J.d.G. A.E. and R.W. performed and analysed the NMR experiments with the assistance of M.C. and J.d.G. X-ray tomography was performed by R.T.W., J.L. and T.R. A.J.L. performed the safety characterization with the assistance of J.d.G. Z.D. performed the ultrasonic transmission mapping measurements. R.P., S.J.H.C. and S.H. contributed to useful discussions. A.J.L., A.E. and J.R.D. prepared the manuscript with input from all other co-authors.

Corresponding author

Correspondence to J. R. Dahn.

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Competing interests

R.W., R.P., S.H. and S.J.H.C. are employed by Tesla Canada R&D. R.T.W., J.L. and T.R. are employed by Carl Zeiss Microscopy.

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Supplementary information

Supplementary Information

Supplementary Table 1, Figs. 1–16 and discussion.

Supplementary Video 1

Submerge and observe qualitative reactivity test pictured in Fig. 6. Charged negative electrode (graphite and plated lithium) samples retrieved from cycled pouch cells at the top of charge are submerged into water to observe their reactivity. The electrolyte chemistries used in the pouch cells from which these samples were retrieved are indicated in the video titles before each submersion.

Supplementary Video 2

Nail test videos pictured in Fig. 6. Anode-free pouch cells at the top of charge after being cycled 50 times were penetrated with nail. The electrolyte chemistries used in each pouch cell nailed are indicated in the video titles before each experiment.

Supplementary Data

Source data for Supplementary Figs. 1 and 2.

Source data

Source Data Fig. 2

Source data Fig. 2.

Source Data Fig. 3

Source data Fig. 3.

Source Data Fig. 6

Source data Fig. 6.

Source Data Fig. 7

Source data Fig. 7.

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Louli, A.J., Eldesoky, A., Weber, R. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat Energy 5, 693–702 (2020). https://doi.org/10.1038/s41560-020-0668-8

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