Material Design Strategy for Halide Solid Electrolytes Li3MX6 (X = Cl, Br, and I) for All-Solid-State High-Voltage Li-Ion Batteries

Kim, Kwangnam; Park, Dongsu; Jung, Hun-Gi; Chung, Kyung Yoon; Shim, Joon Hyung; Wood, Brandon C.; Yu, Seungho

doi:10.1021/acs.chemmater.1c00555

Title: Material Design Strategy for Halide Solid Electrolytes Li₃MX₆ (X = Cl, Br, and I) for All-Solid-State High-Voltage Li-Ion Batteries

Journal Article · Wed May 12 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c00555· OSTI ID:1810664

^[1]; Park, Dongsu ^[2];

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^[1];

^[3]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Korea Inst. of Science and Technology, Seoul (South Korea). Center for Energy Storage Research; Korea Univ., Seoul (South Korea)
Korea Inst. of Science and Technology, Seoul (South Korea). Center for Energy Storage Research; Korea Univ. of Science and Technology, Seoul (South Korea)
Korea Univ., Seoul (South Korea)

Although several solid electrolyte (SE) candidates have been explored, achieving the necessary combination of performance, stability, and processability has been challenging. Recently, several lithium ternary halides have attracted increasing attention for SEs because of their favorable combination of high ionic conductivity and wide electrochemical window. This study aims to provide a material design strategy for lithium halides Li₃MX₆ (X = Cl, Br, and I) for high-voltage all-solid-state Li-ion batteries, achieved by the systematic investigation of crystal structures, phase and electrochemical stabilities, electronic and mechanical properties, and ionic conductivities. Calculation results reveal that the electronegativity difference between M and X affects structural properties and stabilities. Weak Coulomb interactions in Li₃MX₆ result in the preference of the monoclinic phase, and the oxidation potential and chemical stability against the cathode materials of Li₃MX₆ increase for relatively small X. Chlorides exhibit the highest oxidation potential (~4.3 V) among Li₃MX₆, suggesting that chlorides are appropriate SEs for high-voltage cathodes. The band gap and elastic moduli increase for relatively small X, suggesting the relatively low electronic conductivity and elastic deformability of chlorides. Chlorides with transition metals typically exhibit trigonal phases, a wider electrochemical stability window, a larger band gap, and higher elastic moduli compared to other types of halides. Additionally, chloride Li₃MCl₆ is expected to have relatively high ionic conductivities with the aliovalent substitution of M³⁺ to Zr⁴⁺ and the anion mixing of Cl with Br. The findings of this study will provide fundamental guidelines for the development of lithium halide SEs for high-voltage all-solid-state Li-ion batteries.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; National Research Foundation of Korea (NRF)

Grant/Contract Number:: AC52-07NA27344; 2017M1A2A2044482

OSTI ID:: 1810664

Report Number(s):: LLNL-JRNL-819471; 1030326

Journal Information:: Chemistry of Materials, Vol. 33, Issue 10; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Material Design Strategy for Halide Solid Electrolytes Li3MX6 (X = Cl, Br, and I) for All-Solid-State High-Voltage Li-Ion Batteries

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Title: Material Design Strategy for Halide Solid Electrolytes Li₃MX₆ (X = Cl, Br, and I) for All-Solid-State High-Voltage Li-Ion Batteries