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Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography

Abstract

Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behaviour and stability at solid–solid interfaces remains limited compared to at solid–liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth and volumetric changes determines cell behaviour. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur owing to partial molar volume mismatches at either electrode. These results provide insight into how chemo-mechanical phenomena can affect cell performance, thus facilitating the development of solid-state batteries.

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Fig. 1: Operando X-ray imaging of cells at two current densities.
Fig. 2: Analysis of interphase growth and electrochemical behaviour.
Fig. 3: Evolution of voids at the Li/LSPS interface.
Fig. 4: Relating interfacial contact area to cell electrochemistry.
Fig. 5: Displacements and volume changes within a cell.

Data availability

Source data are provided with this paper. All other data that support results in this Article are available from the corresponding author upon reasonable request.

Code availability

MATLAB codes developed for segmentation and analysis of tomographic data in this paper are available from the corresponding author upon reasonable request.

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Acknowledgements

This work is partially supported by the National Science Foundation under Award No. DMR-1652471. M.T.M. acknowledges support from a Sloan Research Fellowship in Chemistry from the Alfred P. Sloan Foundation. J.A.L. acknowledges support from a NASA Space Technology Research Fellowship. F.J.Q.C. acknowledges support from the Colciencias-Fulbright scholarship programme cohort 2016. C.L. and H.L. acknowledge support from the Ministry of Trade, Industry & Energy/Korea Institute of Energy Technology Evaluation and Planning (MOTIE/KETEP) (20194010000100). A portion of this work is supported by the Air Force Office of Scientific Research (AFOSR) under Grant FA9550-17-1-0130. P.P.M. acknowledges financial support from a Scialog programme sponsored jointly by the Research Corporation for Science Advancement and the Alfred P. Sloan Foundation, which includes a grant to Purdue University by the Alfred P. Sloan Foundation. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

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M.T.M., J.A.L. and F.J.Q.C. conceived the study. J.A.L., F.J.Q.C., Y.L. and T.S.M. conducted the operando X-ray tomography experiments. J.A.L., J.C.M. and J.T. designed and tested the cell housings, with C.S. guiding the preliminary imaging experiments. J.A.L. and D.P. conducted the preliminary ex situ cycling experiments. S.Y.H. and C.L. developed pressure measurements for the cell housings. P.P.S. created the three-dimensional renderings. F.D.C. and P.S. assisted with the use of beamline 2-BM and reconstruction processing. A.V., B.S.V. and P.P.M. developed the electrochemical model. J.A.L. and F.J.Q.C. segmented and analysed the data, and also wrote the manuscript with M.T.M. All authors commented on the manuscript.

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Correspondence to Matthew T. McDowell.

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Peer review information Nature Materials thanks Ying Meng and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–21, methods and refs 1 and 2.

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Numerical data for plot in Fig. 5.

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Lewis, J.A., Cortes, F.J.Q., Liu, Y. et al. Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography. Nat. Mater. 20, 503–510 (2021). https://doi.org/10.1038/s41563-020-00903-2

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