Park, Dongsu Park, Haesun Lee, Yongheum Kim, Sang-Ok Jung, Hun-Gi Chung, Kyung Yoon Shim, Joon Hyung Yu, Seungho 2024-01-19T17:02:05Z 2024-01-19T17:02:05Z 2021-09-02 2020-08 1944-8244 https://pubs.kist.re.kr/handle/201004/118317 The development of solid electrolytes (SEs) is a promising pathway to improve the energy density and safety of conventional Li ion batteries. Several lithium chloride SEs, Li3MCl6 (M = Y, Er, In, and Sc), have gained popularity due to their high ionic conductivity, wide electrochemical window, and good chemical stability. This study systematically investigated 17 Li3MCl6 SEs to identify novel and promising lithium chloride SEs. Calculation results revealed that 12 Li3MCl6 (M = Bi, Dy, Er, Ho, In, Lu, Sc, Sm, Tb, TI, Tm, and Y) were stable phase with a wide electrochemical stability window and excellent chemical stability against cathode materials and moisture. Li-ion transport properties were examined using bond valence site energy (BVSE) and ab initio molecular dynamics (AIMD) calculation. Li3MCl6 showed the lower migration energy barrier in monoclinic structures, while orthorhombic and trigonal structures exhibited higher energy barriers due to the sluggish diffusion along the two-dimensional path based on the BVSE model. AIMD results confirmed the slower ion migration along the 2D path, exhibiting lower ionic diffusivity and higher activation energy in orthorhombic and trigonal structures. For the further increase of ionic conductivity in monoclinic structures, Li-ion vacancy was formed by the substitution of M3+ with Zr4+. Zr-substituted phase (Li2.5M0.5Zr0.5Cl6, M = In, Sc) exhibited up to a fourfold increase in ionic conductivity. This finding suggested that the optimization of Li vacancy in the Li3MCl6 SEs could lead to superionic Li3MCl6 SEs. English American Chemical Society Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries Article 10.1021/acsami.0c07003 1 ACS Applied Materials & Interfaces, v.12, no.31, pp.34806 - 34814 ACS Applied Materials & Interfaces 12 31 34806 34814 N scie scopus 000558792700031 2-s2.0-85089711981 Nanoscience & Nanotechnology Materials Science, Multidisciplinary Science & Technology - Other Topics Materials Science Article HIGH-ENERGY LI CHALLENGES CRYSTAL ELECTROLYTE STABILITY energy storage all-solid-state batteries solid electrolytes chloride solid electrolytes materials design