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Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells

Abstract

Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short circuits at high rates of charge, is one of the greatest barriers to realizing high-energy-density all-solid-state lithium-anode batteries. Utilizing in situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/Li6PS5Cl/Li cell as a function of the charge passed. On plating, cracking initiates with spallation, conical ‘pothole’-like cracks that form in the ceramic electrolyte near the surface with the plated electrode. The spallations form predominantly at the lithium electrode edges where local fields are high. Transverse cracks then propagate from the spallations across the electrolyte from the plated to the stripped electrode. Lithium ingress drives the propagation of the spallation and transverse cracks by widening the crack from the rear; that is, the crack front propagates ahead of the Li. As a result, cracks traverse the entire electrolyte before the Li arrives at the other electrode, and therefore before a short circuit occurs.

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Fig. 1: In situ phase-contrast XCT of a Li/Li6PS5Cl/Li cell showing lithium plating-induced spallation.
Fig. 2: Maximum normal 3D strain map from digital volume correlation analysis.
Fig. 3: In situ phase-contrast XCT virtual cross-sections during a single plating of a Li/Li6PS5Cl/Li cell and analysis of lithium deposition in the cracks showing that cracks propagate ahead of Li.
Fig. 4: The 3D volume rendered images from the in situ XCT of cracks and deposited lithium inside the crack upon lithium plating, showing crack propagation ahead of lithium penetration.
Fig. 5: Diffraction mapping showing distribution of lithium dendrites preferentially at the electrode edges and their association with the spallation cracks.
Fig. 6: Slices and volume rendered image from in situ XCT revealing the correlation between spallation and pre-existing pores inside the electrolyte.

Data availability

Supporting research data have been deposited in the Oxford Research Archive and are available at https://doi.org/10.5287/bodleian:9Rn6n6o15.

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Acknowledgements

P.G.B. is indebted to the Faraday Institution All-Solid-State Batteries with Li and Na Anodes (FIRG007, FIRG008), 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. G.L. and C.W.M. acknowledge the Faraday Institution Multiscale Modelling (FIRG003) and the UK Industrial Strategy Challenge Fund: Materials Research Hub for Energy Conversion, Capture, and Storage, under grant EP/R023581/1, for financial support. J.I. is supported by the Swiss National Science Foundation (no. PZ00P2_179886). We thank Paul Scherrer Institut, Villigen, Switerland, and Diamond Light Source, Harwell, United Kingdom, for provision of synchrotron radiation beam time (experiment no. 20182142) at the TOMCAT beamline X02DA of the Swiss Light Source, and beam time (experiment no. EE20795-1) at the I12 beamline of the Diamond Light Source. We acknowledge technical and experimental support at the TOMCAT by A. Bonnin and J. Ihli, and at the I12 by O. Magdysyuk.

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Z.N. contributed to all aspects of the research. Z.N., D.S.J., J.I. and A.B. carried out the in situ phase-contrast synchrotron XCT. Z.N., D.S.J., R.D.M., S.D.P., Y.C. and O.M. carried out the in situ synchrotron XCT–diffraction mapping. Z.N. and J.K. performed synthesis of Li6PS5Cl and powder X-ray diffraction characterization. Z.N. and S.D.P. performed the scanning electron microscopy experiment. G.L. and C.W.M. conducted the finite element analysis of current density distribution. Z.N., D.S.J., R.D.M., S.D.P., Y.C., C.G., B.L., P.A., D.M., G.O.H., T.J.M. and P.G.B. interpreted the data. Z.N. and P.G.B. wrote the manuscript with contributions and revisions from all authors. The project was supervised by T.J.M. and P.G.B.

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Correspondence to Peter G. Bruce.

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Ning, Z., Jolly, D.S., Li, G. et al. Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells. Nat. Mater. 20, 1121–1129 (2021). https://doi.org/10.1038/s41563-021-00967-8

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