Configurational and Dynamical Heterogeneity in Superionic Li5.3PS4.3Cl1.7−xBrx

Pengbo Wang; Sawankumar Patel; Haoyu Liu; Po Hsiu Chien; Xuyong Feng; Lina Gao; Benjamin Chen; Jue Liu; Yan Yan Hu

doi:10.1002/adfm.202307954

Configurational and Dynamical Heterogeneity in Superionic Li_5.3PS_4.3Cl_1.7−_xBr_x

Pengbo Wang, Sawankumar Patel, Haoyu Liu, Po Hsiu Chien, Xuyong Feng, Lina Gao, Benjamin Chen, Jue Liu, Yan Yan Hu

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Abstract

The correlation between lattice chemistry and cation migration in high-entropy Li⁺ conductors is not fully understood due to challenges in characterizing anion disorder. To address this issue, argyrodite family of Li⁺ conductors, which enables structural engineering of the anion lattice, is investigated. Specifically, new argyrodites, Li_5.3PS_4.3Cl_1.7−_xBr_x (0 ≤ x ≤ 1.7), with varying anion entropy are synthesized and X-ray diffraction, neutron scattering, and multinuclear high-resolution solid-state nuclear magnetic resonance (NMR) are used to determine the resulting structures. Ion and lattice dynamics are determined using variable-temperature multinuclear NMR relaxometry and maximum entropy method analysis of neutron scattering, aided by constrained ab initio molecular dynamics calculations. 15 atomic configurations of anion arrangements are identified, producing a wide range of local lattice dynamics. High entropy in the lattice structure, composition, and dynamics stabilize otherwise metastable Li-deficient structures and flatten the energy landscape for cation migration. This resulted in the highest room-temperature ionic conductivity of 26 mS cm⁻¹ and a low activation energy of 0.155 eV realized in Li_5.3PS_4.3Cl_0.7Br, where anion disorder is maximized. This study sheds light on the complex structure–property relationships of high-entropy superionic conductors, highlighting the significance of heterogeneity in lattice dynamics.

Original language	English
Article number	2307954
Journal	Advanced Functional Materials
Volume	33
Issue number	51
DOIs	https://doi.org/10.1002/adfm.202307954
State	Published - Dec 15 2023

Funding

P.W. and S.P. contributed equally to this work. The authors acknowledge the support from the National Science Foundation under grant no. DMR-1847038 and from the NSF MRSEC program (NSF DMR-1720139). All solid-state NMR experiments were performed at the National High Magnetic Field Laboratory. The National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-1644779 and the State of Florida. 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. The authors thank Dr. Zhehong Gan for the helpful discussion on the processing and analysis of the 3QMAS 35Cl NMR. P.W. and S.P. contributed equally to this work. The authors acknowledge the support from the National Science Foundation under grant no. DMR‐1847038 and from the NSF MRSEC program (NSF DMR‐1720139). All solid‐state NMR experiments were performed at the National High Magnetic Field Laboratory. The National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR‐1644779 and the State of Florida. 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. The authors thank Dr. Zhehong Gan for the helpful discussion on the processing and analysis of the 3QMAS Cl NMR. 35

Keywords

high entropy
lattice dynamics
mixed anion
solid-state nuclear magnetic resonance
superionic conductors

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10.1002/adfm.202307954

Cite this

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title = "Configurational and Dynamical Heterogeneity in Superionic Li5.3PS4.3Cl1.7−xBrx",

abstract = "The correlation between lattice chemistry and cation migration in high-entropy Li+ conductors is not fully understood due to challenges in characterizing anion disorder. To address this issue, argyrodite family of Li+ conductors, which enables structural engineering of the anion lattice, is investigated. Specifically, new argyrodites, Li5.3PS4.3Cl1.7−xBrx (0 ≤ x ≤ 1.7), with varying anion entropy are synthesized and X-ray diffraction, neutron scattering, and multinuclear high-resolution solid-state nuclear magnetic resonance (NMR) are used to determine the resulting structures. Ion and lattice dynamics are determined using variable-temperature multinuclear NMR relaxometry and maximum entropy method analysis of neutron scattering, aided by constrained ab initio molecular dynamics calculations. 15 atomic configurations of anion arrangements are identified, producing a wide range of local lattice dynamics. High entropy in the lattice structure, composition, and dynamics stabilize otherwise metastable Li-deficient structures and flatten the energy landscape for cation migration. This resulted in the highest room-temperature ionic conductivity of 26 mS cm−1 and a low activation energy of 0.155 eV realized in Li5.3PS4.3Cl0.7Br, where anion disorder is maximized. This study sheds light on the complex structure–property relationships of high-entropy superionic conductors, highlighting the significance of heterogeneity in lattice dynamics.",

keywords = "high entropy, lattice dynamics, mixed anion, solid-state nuclear magnetic resonance, superionic conductors",

author = "Pengbo Wang and Sawankumar Patel and Haoyu Liu and Chien, {Po Hsiu} and Xuyong Feng and Lina Gao and Benjamin Chen and Jue Liu and Hu, {Yan Yan}",

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