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Direct in situ measurements of electrical properties of solid–electrolyte interphase on lithium metal anodes

Nature Energy volume 8, pages 1345–1354 (2023)Cite this article

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Abstract

The solid–electrolyte interphase (SEI) critically governs the performance of rechargeable batteries. An ideal SEI is expected to be electrically insulative to prevent persistently parasitic reactions between the electrode and the electrolyte and ionically conductive to facilitate Faradaic reactions of the electrode. However, the true nature of the electrical properties of the SEI remains hitherto unclear due to the lack of a direct characterization method. Here we use in situ bias transmission electron microscopy to directly measure the electrical properties of SEIs formed on copper and lithium substrates. We reveal that SEIs show a voltage-dependent differential conductance. A higher rate of differential conductance induces a thicker SEI with an intricate topographic feature, leading to an inferior Coulombic efficiency and cycling stability in Li||Cu and Li||LiNi0.8Mn0.1Co0.1O2 cells. Our work provides insight into the targeted design of the SEI with desired characteristics towards better battery performance.

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Fig. 1: In situ bias TEM measurement of electrical properties of the SEI.
Fig. 2: Simulation of the SEI structure and subsequent calculation of I–V curve.
Fig. 3: Electrical properties of SEI and electrochemical cell performances.
Fig. 4: Dependence of microstructure of Li deposits on rate of differential conductance.
Fig. 5: Correlation between SEI structure and its electrical property.

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Acknowledgements

We thank Y. Wu at Pacific Northwest National Laboratory (PNNL) for providing the TiO2 sample and C. Yan at University of Chicago for helpful discussions about electrical measurement. This work was supported by the Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) under the Advanced Battery Materials Research (BMR) Program and the US–Germany Cooperation on Energy Storage under Contract DE-LC-000L072 (C.W. and W.X.). P.B.B. and J.M.S. acknowledge the US–Germany Cooperation on Energy Storage under Contract DE-AC02-05CH11357 and the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US DOE through the BMR Program (Battery500 Consortium phase 2) under DOE contract DE-AC05-76RL01830 from PNNL. Computational resources from the Texas A&M University High Performance Research Computing are gratefully acknowledged. The characterization work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the US DOE under contract DE-AC05-76RL01830. The work at the molecular foundry, Lawrence Berkeley National Laboratory was supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract DE-AC02-05CH11231. G.R. and J.L. acknowledge US National Institutes of Health grants R01HL115153, R01GM104427, R01MH077303 and R01DK042667.

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Author notes

  1. These authors contributed equally: Yaobin Xu, Hao Jia.

Authors and Affiliations

  1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA

    Yaobin Xu, Mark H. Engelhard, Shuang Li & Chongmin Wang

  2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Hao Jia, Xia Cao, Phung M. L. Le, Ji-Guang Zhang & Wu Xu

  3. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Peiyuan Gao

  4. Department of Chemical Engineering, Texas A&M University, College Station, TX, USA

    Diego E. Galvez-Aranda, Saul Perez Beltran, Jorge M. Seminario & Perla B. Balbuena

  5. Department of Electrical and Computer Engineering, Texas A&M University, College Station, TX, USA

    Diego E. Galvez-Aranda & Jorge M. Seminario

  6. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jianfang Liu & Gang Ren

  7. Department of Materials Science and Engineering, Texas A&M University, College Station, TX, USA

    Jorge M. Seminario & Perla B. Balbuena

  8. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Perla B. Balbuena

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  1. Yaobin Xu
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Contributions

C.W. and Y.X. conceived the project and designed the experiments with suggestions from W.X. and H.J. Y.X. collected and analysed experimental data for in situ TEM and cryo-TEM studies and drafted the paper under the direction of C.W. and W.X. H.J. performed the electrochemical measurements. P.G. performed the AIMD calculation of bulk electrolytes. D.E.G.-A. and J.M.S. performed the SEI composition analyses, the molecular orbital electronic structure calculations and the current–voltage characteristics of the SEI samples. S.P.B. and P.B.B. performed hybrid AIMD combined with reactive force field simulations. J.L. and G.R. carried out three-dimensional reconstruction. X.C. conducted battery cycling tests. P.M.L.L. and J.-G.Z. helped with interpretation of the electrochemical data. M.H.E. collected XPS data. S.L. prepared the W STM tip. Y.X., H.J., W.X. and C.W. co-wrote the original paper. All authors discussed the results and edited the paper.

Corresponding authors

Correspondence to Jorge M. Seminario, Perla B. Balbuena, Wu Xu or Chongmin Wang.

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Supplementary Information

Supplementary Figs. 1–42, Methods, Discussion and Tables 1–9.

Supplementary Video 1

Three-dimensional reconstruction of Li deposits formed in LCE, PLHCE, HCE and LHCE.

Source data

Source Data Fig. 3

Statistical source data for Fig. 3a–c.

Source Data Fig. 5

Statistical source data for Fig. 5c.

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Xu, Y., Jia, H., Gao, P. et al. Direct in situ measurements of electrical properties of solid–electrolyte interphase on lithium metal anodes. Nat Energy 8, 1345–1354 (2023). https://doi.org/10.1038/s41560-023-01361-1

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