Kim, Ji-Su Kim, Young Jung Han, Daseul Nam, Kyung-Wan Kwon, Gihan Heo, Tae Wook Jung, Hun-Gi Yoon, Kyung Joong Kim, Hyoungchul 2024-01-19T09:34:44Z 2024-01-19T09:34:44Z 2023-04-13 2023-04 2050-7488 https://pubs.kist.re.kr/handle/201004/113838 Amorphous sulfides are among the most promising candidates for solid electrolytes (SEs) owing to their excellent deformability and acceptable Li-ion conductivity (sigma(ion)) 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. 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 sigma(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 PS43- molecular anions in a Li2S-P2S5-based glass SE. At a specific Br content, [(Li2S)(0.658)(LiI0.9LiBr0.1)(0.342)](0.825)[P2S5](0.175) recorded a sigma(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 sigma(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. English Royal Society of Chemistry Structural mapping and tuning of mixed halide ions in amorphous sulfides for fast Li-ion conduction and high deformability Article 10.1039/d2ta09585h 1 Journal of Materials Chemistry A, v.11, no.14, pp.7457 - 7467 Journal of Materials Chemistry A 11 14 7457 7467 N scie scopus 000953601900001 2-s2.0-85151041201 Chemistry, Physical Energy & Fuels Materials Science, Multidisciplinary Chemistry Energy & Fuels Materials Science Article; Early Access TOTAL-ENERGY CALCULATIONS SUPERIONIC GLASSES ELASTIC PROPERTIES LI2S-P2S5 GLASSES ROOM-TEMPERATURE OXIDE SEMICONDUCTORS PRINCIPLES ORDER NMR