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Direct correlation between void formation and lithium dendrite growth in solid-state electrolytes with interlayers

Nature Materials volume 21, pages 1050–1056 (2022)Cite this article

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Abstract

Solid-state Li-ion batteries with lithium anodes offer higher energy densities and are safer than conventional liquid electrolyte-based Li-ion batteries. However, the growth of lithium dendrites across the solid-state electrolyte layer leads to the premature shorting of cells and limits their practical viability. Here, using solid-state Li half-cells with metallic interlayers between a garnet-based lithium-ion conductor and lithium, we show that interfacial void growth precedes dendrite nucleation and growth. Specifically, void growth was observed at a current density of around two-thirds of the critical current density for dendrite growth. Computational calculations reveal that interlayer materials with higher critical current densities for dendrite growth also have the largest thermodynamic and kinetic barriers for lithium vacancy accumulation at their interfaces with lithium. Our results suggest that interfacial modification with suitable metallic interlayers decreases the tendency for void growth and improves dendrite growth tolerance in solid-state electrolytes, even in the absence of high stack pressures.

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Fig. 1: Interfacial current density distribution at Li/SSE interfaces.
Fig. 2: Li nucleation overpotential for deposition on Al and W.
Fig. 3: Critical current density determination for cells with Al and W ILs.
Fig. 4: Temperature-dependent electrochemical performance of cells with ILs.
Fig. 5: Current density-dependent void growth in cells with ILs.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported in part by grants from the Indian Space Research Organization (ISRO; grant no. ISTC/CSS/NPH/397), the Department of Heavy Industries (DHI), India, the Department of Science and Technology, India, through the DST-IISc Energy Storage Platform on Supercapacitors and Power Dense Devices under the MECSP-2K17 program (grant no. DST/TMD/MECSP/2K17/20) and by the Advanced Research Projects Agency-Energy Integration and Optimization of Novel Ion Conducting Solids (IONICS) programme (grant no. DE-AR0000774). V.R. acknowledges access to common facilities at CeNSE and SSCU. N.P.B.A. acknowledges the new faculty start-up grant (no. 12-0205-0618-77) provided by the Indian Institute of Science (IISc) and funding through the early career research award (grant no. ECR/2018/001047) of the Science and Engineering Research Board, Department of Science and Technology, India. The Extreme Science and Engineering Discovery Environment (XSEDE) is acknowledged for providing computational resources (award no. TG-CTS180061)41.

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Authors and Affiliations

  1. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, India

    Vikalp Raj, Varun R. Kankanallu, Bibhatsu Kuiri & Naga Phani B. Aetukuri

  2. Department of Mechanical Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

    Victor Venturi & Venkatasubramanian Viswanathan

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Contributions

N.P.B.A. designed and directed the work. V.R. and V.R.K. performed the experiments and analysed the experimental data. B.K. performed COMSOL simulations. V. Viswanathan directed the DFT and NEB studies. V. Venturi designed and performed the DFT and NEB modelling. All authors contributed to the writing of the manuscript.

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Correspondence to Naga Phani B. Aetukuri.

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Competing interests

V.R., V.R.K. and N.P.B.A. are declared inventors on patent application number PCT/IB2020/058463 submitted by the Indian Institute of Science on the use of these ILs for high energy density batteries. V. Viswanathan is a technical consultant at QuantumScape Corporation.

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Nature Materials thanks Partha Mukherjee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Interfacial characterization of Al and W interlayer interfaces.

Cross-sectional SEM images of (a) Li/LLZTO (b) Li/Al/LLZTO and (c) Li/W/LLZTO interfaces. Discontinuities can be seen in the SEM image for Li/LLZTO interface, but not for the Li/Al/LLZTO or Li/W/LLZTO interfaces. The scale bars in all images correspond to a length of 20 µm.

Extended Data Fig. 2 Al and W slabs used for computational calculations.

Li monolayers on (100) surface facets of Al (a, b) and W (c, d). Top views are shown in panels (a) and (c), and side views are in panels (b) and (d).

Supplementary information

Supplementary Information

Supplementary Sections 1.1–1.8, Figs. 1–27, Tables 1 and 2, and references.

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Raj, V., Venturi, V., Kankanallu, V.R. et al. Direct correlation between void formation and lithium dendrite growth in solid-state electrolytes with interlayers. Nat. Mater. 21, 1050–1056 (2022). https://doi.org/10.1038/s41563-022-01264-8

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