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Dendrite initiation and propagation in lithium metal solid-state batteries

Nature volume 618, pages 287–293 (2023)Cite this article

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Abstract

All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today’s Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5,6,7,8,9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.

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Fig. 1: Operando XCT virtual cross-sections during plating of a Li/Li6PS5Cl/Li cell showing the development of a dendrite crack from initiation through propagation to complete short circuit. Combined FIB-SEM with SIMS as well as mass spectrometry provides evidence supporting the presence of Li in subsurface regions of the solid electrolyte.
Fig. 2: Schematics and implications of the dendritic crack initiation process. Higher current density leads to greater pressure in the pore, with cracking occurring when the pressure exceeds the local (grain boundary) fracture strength of the solid electrolyte.
Fig. 3: Dendrite crack propagation. Longer Li dendrites, higher currents and greater stack pressures promote crack propagation. Li dendrites do not need to fill a crack completely to meet the fracture criterion required for crack lengthening.
Fig. 4: Propagation of a Li dendrite under various stack pressures. Larger stack pressures reduce the number of cycles to short circuit. Removal of applied stack pressure can enable prolonged cycling.

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Data availability

The datasets generated and/or analysed during this study are available from the corresponding author on reasonable request.

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The computer code generated and used during this study is available from the corresponding author on reasonable request.

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Acknowledgements

P.G.B. is indebted to the Faraday Institution SOLBAT (FIRG007, FIRG008, FIRG026), as well as the Engineering and Physical Sciences Research Council, Enabling Next Generation Lithium Batteries (EP/M009521/1), the University of Oxford experimental equipment upgrade (EP/M02833X/1) and the Henry Royce Institute for Advanced Materials (EP/R0066X/1, EP/S019367/1, EP/R010145/1) for financial support. We thank the Diamond Light Source for the provision of synchrotron radiation beam time (experiment no. MG23980-1) at the I13-2 beamline at the Diamond Light Source. We acknowledge technical and experimental support at the I13-2 beamline by A. J. Bodey.

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  1. These authors contributed equally: Ziyang Ning, Guanchen Li, Dominic L. R. Melvin

Authors and Affiliations

  1. Department of Materials, University of Oxford, Oxford, UK

    Ziyang Ning, Dominic L. R. Melvin, Yang Chen, Junfu Bu, Dominic Spencer-Jolly, Junliang Liu, Bingkun Hu, Xiangwen Gao, Johann Perera, Chen Gong, Shengda D. Pu, Shengming Zhang, Boyang Liu, Gareth O. Hartley, Richard I. Todd, Patrick S. Grant, David E. J. Armstrong, T. James Marrow & Peter G. Bruce

  2. Fujian Science & Technology Innovation Laboratory for Energy Devices (21C Lab), Ningde, China

    Ziyang Ning

  3. Department of Engineering Science, University of Oxford, Oxford, UK

    Guanchen Li & Charles W. Monroe

  4. James Watt School of Engineering, University of Glasgow, Glasgow, UK

    Guanchen Li

  5. The Faraday Institution, Harwell Campus, Didcot, UK

    Guanchen Li, Dominic L. R. Melvin, Junfu Bu, Dominic Spencer-Jolly, Xiangwen Gao, Boyang Liu, Gareth O. Hartley, Patrick S. Grant, David E. J. Armstrong, Charles W. Monroe & Peter G. Bruce

  6. Department of Mechanical Engineering, University of Bath, Bath, UK

    Yang Chen

  7. Diamond Light Source, Harwell Campus, Didcot, UK

    Andrew J. Bodey

  8. Department of Chemistry, University of Oxford, Oxford, UK

    Peter G. Bruce

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Contributions

Z.N., G.L. and D.L.R.M. contributed to all aspects of the research. Z.N., D.L.R.M., D.S.-J., S.D.P., G.O.H. and A.J.B. carried out the operando synchrotron XCT. Z.N. and D.L.R.M. performed the preparation of electrolyte discs and cell assembly. Z.N., D.L.R.M, C.G. and X.G. performed the on-line mass spectrometry. Z.N., D.L.R.M., B.H., B.L. and J.B. performed the plasma FIB imaging. D.L.R.M. and J.B. performed plasma FIB imaging with SIMS. Z.N., D.L.R.M., J.P., J.L. and D.E.J.A. conducted the preparation of microcantilever and mechanical tests. G.L., Y.C. and C.W.M. conducted the modelling. Z.N., G.L., D.L.R.M., D.S.-J., R.I.T., P.S.G., D.E.J.A., T.J.M., C.W.M. and P.G.B. discussed the data. All authors contributed to the interpretation of data. Z.N., D.L.R.M., G.L., C.W.M. and P.G.B. wrote the manuscript, with contributions and revisions from all authors. The project was supervised by C.W.M., T.J.M. and P.G.B.

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Correspondence to T. James Marrow, Charles W. Monroe or Peter G. Bruce.

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Supplementary information

Supplementary Information

This file contains details of the dendrite initiation and propagation modelling, Supplementary Figs. 1–21 and Supplementary Tables 1–3.

Supplementary Video 1

Operando XCT imaging showing the development of a dendrite crack from initiation through propagation to short circuit.

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Ning, Z., Li, G., Melvin, D.L.R. et al. Dendrite initiation and propagation in lithium metal solid-state batteries. Nature 618, 287–293 (2023). https://doi.org/10.1038/s41586-023-05970-4

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