Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries

Abstract

Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus (Gs) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC’s mechanical properties and the partial molar volume of Li+ (\(V_{\mathrm{Li}^+}\)) relative to those of the lithium anode (GLi and VLi) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly ‘soft’, as is typical of polymer electrolytes, but feature an atypically low \(V_{\mathrm{Li}^+}\) that is more reminiscent of ‘hard’ ceramics. Li plating (1 mA cm−2; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm−2) or high-capacity sulfur cathodes (3.02 mAh cm−2).

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Fig. 1: Classifying SICs within a universal chemomechanical model for dendrite formation during electrodeposition.
Fig. 2: Formulation-dependent architectures, morphologies and mechanical properties for LiF@PIM-1 composites generated in situ by cation metathesis.
Fig. 3: Li ion migration in LESAs.
Fig. 4: Uniform Li metal electrodeposition enabled by dendrite-suppressing LiF@PIM-1 SICs.
Fig. 5: Divergent electrochemical performance of Li–NMC-622 cells assembled with thin Li anodes, highlighting the benefits of dendrite-suppressing LiF@PIM-1 SICs.
Fig. 6: Galvanostatic cycling of Li–S cells, comparing dendrite-suppressing LESAs with artificial SEI-generating electrolyte additives.

Data availability

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

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Acknowledgements

This work was supported by the Advanced Research Projects Agency–Energy Integration and Optimization of Novel Ion Conducting Solids (IONICS) programme under grant no. DE-AR0000774. Z.A. was supported in part by the Phillips and Huang Family Fellowship in Energy from the College of Engineering at Carnegie Mellon University. A.W.E. was supported by the US Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory Internship (SULI) programme. Portions of this work, including polymer synthesis and characterization, were carried out as a User Project at the Molecular Foundry, which is supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. Synchrotron hard X-ray tomography was conducted on beamline 8.3.2 at the Advanced Light Source, which is a DOE Office of Science User Facility under the same contract. NMC-622 cathodes were provided by B.J. Polzin from the Cell Analysis, Modeling and Prototyping (CAMP) Facility at Argonne National Laboratories. The computational portion of this work was performed on the Hercules computer cluster, which was funded through a Carnegie Mellon College of Engineering Equipment grant. We thank Y. Wang, D. Prendergast, D. Parkinson, P. Frischmann, Y.-M. Chiang, P. Albertus, S. Babinec and D. Cagle for helpful discussions.

Author information

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Authors

Contributions

B.A.H. designed and directed the study. C.F. characterized LiF@PIM-1 structure–transport relationships, carried out hard X-ray microtomography, and implemented LiF@PIM-1 composites in Li–NMC cells, with assistance from A.W.E. J.K. characterized LiF@PIM composites in Li–Li symmetric cells (plate-strip tests and EIS from assembly to formation and high-rate cycling) and in Li–S full cells. V.Viswanathan designed and directed the theoretical study. V.Venturi and Z.A. conducted the simulations. B.A.H., V.Venturi, C.F., V.Viswanathan and J.K. wrote the paper, with contributions from all co-authors.

Corresponding author

Correspondence to Brett A. Helms.

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Competing interests

B.A.H. is named as an inventor on PCT patent application 62/431,300 submitted by Lawrence Berkeley National Laboratory that covers these and related classes of solid-ion conductors, as well as aspects of their use in electrochemical devices.

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Extended data

Extended Data Fig. 1 Isosurfaces of charge density on LiF surface during Li hopping.

The charge density is obtained using self-consistent DFT. The Bader volume for each atom is calculated by partitioning the density into zero-flux surfaces.

Extended Data Fig. 2 Ion migration along a cation-rich LiF surface, modeled by adsorbed LiPF6.

The LiPF6 salt had its structure relaxed, and was subsequently placed on top of the LiF slab.

Extended Data Fig. 3 Comparing energy landscapes for Li+ migration along anion- and cation-rich LiF surfaces.

Minimum energy pathways for Li+ motion on both anion and cation-rich LiF surfaces obtained from nudged elastic band (NEB) simulations using the BEEF-vdW functional. The hopping barrier for the cation-rich system was calculated to be 0.14 ± 0.07 eV. Source data

Supplementary information

41563_2020_655_MOESM2_ESM.mp4

Electrolyte permeability tests for LESA-3 and Celgard.

Supplementary Information

Supplementary methods, Figs. 1–12 and Table 1.

Supplementary Video 1

Electrolyte permeability tests for LESA-3 and Celgard.

Source data

Source Data Fig. 2

g, XRD raw data of LESAs and LiF; h, Shear modulus and LiF grain size raw data

Source Data Fig. 3

a, Calculated Li+ hopping energy through LiF surface and bulk; c, EIS raw data of LESA-3 depending on temperature; d, EIS raw data of Celgard depending on temperature; e, Ahrrenius plot source data derived from Fig. 3c, d; f, Galvanostatic polarization source data for LESA-3; g, EIS source data before and after polarization of LESA-3

Source Data Fig. 4

a, Galvanostatic Li|Li symmetric cell cycling source data for LESA-3, PIM-1, and Celgard; b, EIS source data for LESA-3, PIM-1, and Celgard before Li|Li symmetric cell cycling; c, EIS source data after Li|Li symmetric cell cycling for LESA-3, PIM-1, and Celgard.

Source Data Fig. 5

a, Galvanostatic Li-NMC cell cycling raw data of LESA-3; b, Li|NMC cell rate capability source data for LESA-3, PIM-1, and Celgard; c, Li-NMC cell cycling source data for LESA-3, PIM-1, and Celgard

Source Data Fig. 6

a, Galvanostatic Li-S cell cycling source data of LESA-3; b, Galvanostatic Li-S cell cycling source data of Celgard; c, Li-S cell cycling source data for LESA-3 and Celgard

Source Data Extended Data Fig. 3

Calculated activation energy raw data of anion- and cation-rich LiF surface for Li+ hopping

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Fu, C., Venturi, V., Kim, J. et al. Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries. Nat. Mater. (2020). https://doi.org/10.1038/s41563-020-0655-2

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