Structural mapping and tuning of mixed halide ions in amorphous sulfides for fast Li-ion conduction and high deformability

Kim, Ji-Su; Kim, Young Jung; Han, Daseul; Nam, Kyung-Wan; Kwon, Gihan; Heo, Tae Wook; Jung, Hun-Gi; Yoon, Kyung Joong; Kim, Hyoungchul

doi:10.1039/d2ta09585h

Structural mapping and tuning of mixed halide ions in amorphous sulfides for fast Li-ion conduction and high deformability

Journal Article · Mon Mar 20 00:00:00 EDT 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d2ta09585h· OSTI ID:1984410

Kim, Ji-Su ^[1]; Kim, Young Jung ^[1]; Han, Daseul ^[2]; ^[2]; ^[3]; Heo, Tae Wook ^[4]; ^[1]; ^[1]; ^[5]

Korea Institute of Science and Technology, Seoul (Korea, Republic of)
Dongguk Univ., Seoul (Korea, Republic of)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Materials Science Division
Korea Institute of Science and Technology, Seoul (Korea, Republic of); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Materials Science Division

Amorphous sulfides are among the most promising candidates for solid electrolytes (SEs) owing to their excellent deformability and acceptable Li-ion conductivity (σion) at room temperature. However, the complex atomic structure of these amorphous materials without long-range ordering results in a lack of structural understanding and difficulties in tuning material properties. Here, in this study, we performed structural mapping of glassy sulfide SEs composed of various anion clusters using a combinatorial atomic level analysis of synchrotron X-ray-based pair distribution function (PDF) and reverse Monte-Carlo (RMC) methods, demonstrating the potential to tune σ_ion in glass SEs. First, we prepared a new glassy sulfide with a mixed anion framework of two halogens (Br and I) as atomic anions, with PS₄^3- molecular anions in a Li₂S–P₂S₅-based glass SE. At a specific Br content, [(Li₂S)_0.658(LiI_0.9LiBr_0.1)_0.342]_0.825[P₂S₅]_0.175 recorded a σ_ion of 2.27 mS cm^-1, the highest value for any glass sulfides reported to date; however, its elastic modulus was still suppressed to 14.48 GPa. PDF and RMC calculations successfully provided structural mapping of anion clusters, including two halogens. Molecular dynamics simulations of each composition confirmed that flexible coordination caused by the rattling of small polarizable Br ions in the mixed halogens of glassy SEs contributed to the superior σ_ion. Our results may provide new insights into the design of superior glassy SEs that play key roles in all-solid-state batteries requiring fast Li-ion conduction and high deformability.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: Korea Institute of Science and Technology; National Research Foundation of Korea (NRF); USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC52-07NA27344; SC0012704

OSTI ID:: 1984410

Alternate ID(s):: OSTI ID: 2007592
OSTI ID: 1962447

Report Number(s):: BNL--224474-2023-JAAM; LLNL--JRNL-845430

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 14 Vol. 11; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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