Liquid-like solid-state diffusion of lithium ions in super-halide-rich argyrodite

Yubo Wang, J. David Bazak, Laidong Zhou, Qiang Zhang, Baltej Singh, Linda F. Nazar

Research output: Contribution to journalArticlepeer-review

Abstract

The development of solid electrolytes with high ionic conductivity is essential for advancing safer, high-energy-density solid-state batteries, where lithium site distribution in the sublattice strongly affects ion transport. Here, we report a super-halide-rich argyrodite, Li5.3PS4.3Cl1.7, with remarkable room-temperature ionic conductivity (11.4 ± 0.7 mS cm−1) due to population of two additional interstitial lithium sites induced by vacancy redistribution. Prominent lithium density between lithium sites and elevated atomic displacement parameters indicate liquid-like diffusive behavior resembling sublattice melting. Combining electrochemical impedance spectroscopy, pulsed-field gradient NMR, and T1 relaxation methods, we demonstrate that the augmented conductivity partly arises from a low energy barrier (0.08 eV) at the local scale, attributed to a three-site lithium distribution that drives correlated lithium dynamics. This work advances our understanding of the structure-dynamics interplay in super-halide-rich argyrodites, and highlighting their potential as solid-state battery electrolytes in cells with a coated single-crystal NMC82 cathode that achieve 170 mAh/g capacity at a 0.2 C rate.

Original languageEnglish
Article number102314
JournalCell Reports Physical Science
Volume5
Issue number12
DOIs
StatePublished - Dec 18 2024

Funding

This work was supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences. L.F.N. also acknowledges NSERC for platform support via their Canada Research Chair and Discovery Grant programs, and the Ontario Research Fund. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Keywords

  • all-solid-state lithium batteries
  • lithium argyrodite
  • neutron diffraction
  • solid electrolytes
  • sublattice melting

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