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Dendrite formation in solid-state batteries arising from lithium plating and electrolyte reduction

Nature Materials volume 24, pages 581–588 (2025)Cite this article

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Abstract

All-solid-state batteries offer high-energy-density and eco-friendly energy storage but face commercial hurdles due to dendrite formation, especially with lithium metal anodes. Here we report that dendrite formation in Li/Li7La3Zr2O12/Li batteries occurs via two distinct mechanisms, using non-invasive solid-state nuclear magnetic resonance and magnetic resonance imaging. Tracer-exchange nuclear magnetic resonance shows non-uniform Li plating at electrode–electrolyte interfaces and local Li+ reduction at Li7La3Zr2O12 grain boundaries. In situ magnetic resonance imaging reveals rapid dendrite formation via non-uniform Li plating, followed by sluggish bulk dendrite nucleation from Li+ reduction, with an intervening period of stalled growth. Formation of amorphous dendrites and subsequent crystallization, the defect chemistry of solid electrolytes and battery operating conditions play a critical role in shaping the complex interplay between the two mechanisms. Overall, this work deepens our understanding of dendrite formation in solid-state Li batteries and provides comprehensive insight that might be valuable for mitigating dendrite-related challenges.

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Fig. 1: Li microstructure formation in cubic LLZO.
Fig. 2: Two mechanisms of dendrite formation in LLZO validated via tracer-exchange NMR.
Fig. 3: Dendrite distribution in LLZO solid electrolytes.
Fig. 4: In situ MRI detection of dendrite formation and propagation through LLZO.

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Data availability

Data generated or analysed during this study are also included in Supplementary Information. Further data are available from the corresponding authors upon request. Source data are provided with this paper.

Code availability

The Python code used for simulating the tracer-exchange process is provided via GitHub at https://github.com/Jak1022/Python_tracer_exchange.

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Acknowledgements

We acknowledge the support from the National Science Foundation under grant no. DMR-2319151 for Y.C. and Y.-Y.H. All solid-state NMR experiments were performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement nos DMR-1644779 and DMR-2128556. We thank the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences programme for support under award no. DE-SC0019121 for D.H. and H.X. This research used resources of the Center for Nanoscale Materials, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357.

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Author notes

  1. These authors contributed equally: Haoyu Liu, Yudan Chen, Po-Hsiu Chien.

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA

    Haoyu Liu, Yudan Chen, Po-Hsiu Chien, Erica Truong, Ifeoluwa P. Oyekunle & Yan-Yan Hu

  2. Department of Physics, Florida State University, Tallahassee, FL, USA

    Ghoncheh Amouzandeh

  3. Center for Interdisciplinary Magnetic Resonance, National High Magnetic Field Laboratory, Tallahassee, FL, USA

    Ghoncheh Amouzandeh, Peter L. Gor’kov, Jens T. Rosenberg, Samuel C. Grant & Yan-Yan Hu

  4. Micron School of Materials Science and Engineering, Boise State University, Boise, ID, USA

    Dewen Hou & Hui Xiong

  5. Center for Nanoscale Materials, Argonne National Laboratory, Lemont, IL, USA

    Dewen Hou

  6. Department of Chemical and Biomedical Engineering, FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL, USA

    Jamini Bhagu, Samuel W. Holder & Samuel C. Grant

Authors
  1. Haoyu Liu
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Contributions

Y.-Y.H. conceived the concept, designed the experiments and supervised the project. S.C.G. directed and supervised the MRI component of the study. H.L., Y.C. and P.-H.C. performed LLZO synthesis, X-ray diffraction characterization, symmetrical cell assembly and electrochemical measurements. H.L., Y.C., P.-H.C. and E.T. carried out 6,7Li NMR. H.L. and Y.C. performed numerical simulations and Li isotope composition analysis of cycled samples. S.C.G., J.T.R., H.L., Y.C., P.-H.C., G.A., I.P.O., J.B., S.W.H. and Y.-Y.H. performed MRI and data analysis. P.L.G. developed the MRI gradient coil for in situ 2D MRI. D.H. and H.X. contributed to TEM and energy-filtered TEM data acquisition and analysis. Y.-Y.H., H.L., Y.C. and P.-H.C. wrote the paper with contributions from all co-authors.

Corresponding authors

Correspondence to Samuel C. Grant or Yan-Yan Hu.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–10 and Scheme 1.

Source data

Source Data Fig. 1

Cycling voltage profile, solid-state NMR and EPR data.

Source Data Fig. 2

The solid-state NMR and material composition data.

Source Data Fig. 4

Cycling voltage profile and dendrite formation data.

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Liu, H., Chen, Y., Chien, PH. et al. Dendrite formation in solid-state batteries arising from lithium plating and electrolyte reduction. Nat. Mater. 24, 581–588 (2025). https://doi.org/10.1038/s41563-024-02094-6

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