Liquid-like dynamics in a solid-state lithium electrolyte

Ding, Jingxuan; Gupta, Mayanak K.; Rosenbach, Carolin; Lin, Hung-Min; Osti, Naresh C.; Abernathy, Douglas L.; Zeier, Wolfgang G.; Delaire, Olivier

doi:10.1038/s41567-024-02707-6

Title: Liquid-like dynamics in a solid-state lithium electrolyte

Journal Article · 05 January 2025 · Nature Physics

DOI: https://doi.org/10.1038/s41567-024-02707-6 · OSTI ID:2502159

Ding, Jingxuan ^[1];

^[2]; Rosenbach, Carolin ^[3];

^[4];

^[5];

^[6];

^[4]

Duke Univ., Durham, NC (United States); Harvard Univ., Cambridge, MA (United States)
Duke Univ., Durham, NC (United States); Bhabha Atomic Research Centre Mumbai, MH (India)
University of Münster (Germany)
Duke Univ., Durham, NC (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
University of (Germany); Forschungszentrum Juelich, Münster (Germany). Inst. for Energy and Climate Research (IEK)

Superionic materials represent a regime intermediate between the crystalline and liquid states of matter. Despite the considerable interest in potential applications for solid-state batteries or thermoelectric devices, it remains unclear whether the fast ionic diffusion observed in superionic materials reflects liquid-like dynamics or whether the hops of mobile ions are inherently coupled to more conventional lattice phonons. Here we reveal a crossover from crystalline vibrations to relaxational dynamics of ionic diffusion in the superionic compound Li₆PS₅Cl, a candidate solid-state electrolyte. By combining inelastic and quasi-elastic neutron-scattering measurements with first-principles-based machine-learned molecular dynamics simulations, we found that the vibrational density of states in the superionic state strongly deviates from the quadratic behaviour expected from the Debye law of lattice dynamics. The superionic dynamics emerges from overdamped phonon quasiparticles to give rise to a linear density of states characteristic of instantaneous normal modes in the liquid state. Further, we showed that the coupling of lattice phonons with a dynamic breathing of the Li+ diffusion bottleneck enables an order-of-magnitude increase in diffusivity. Thus, our results shed insights into superionics for future energy storage and conversion technologies.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: German Research Foundation (DFG); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 2502159

Journal Information:: Nature Physics, Journal Name: Nature Physics Journal Issue: 1 Vol. 21; ISSN 1745-2473

Publisher:: Nature Publishing Group (NPG)Copyright Statement

Country of Publication:: United States

Language:: English

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