Tailoring Ion Transport in Li3-3yHo1+yCl6-xBrx via Transition-Metal Free Structural Planes and Charge Carrier Distribution

• Published in: Advanced science 2024-12, p.e2409668
• Main Authors: Ogbolu, Bright O, Poudel, Tej P, Dikella, Thilina N D D, Truong, Erica, Chen, Yudan, Hou, Dewen, Li, Tianyi, Liu, Yuzi, Gabriel, Eric, Xiong, Hui, Huang, Chen, Hu, Yan-Yan
• Format: Article
• Language: English
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202409668

Localized atomistic disorder in halide-based solid electrolytes (SEs) can be leveraged to boost Li+ mobility. In this study, Li+ transport in structurally modified Li3HoCl6, via Br- introduction and Li+ deficiency, is explored. The optimized Li3-3 yHo1+ yCl6- xBrx achieves an ionic conductivity of 3.8 mS cm-1 at 25 °C, the highest reported for holmium halide materials. 6,7Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li+ motional rate neighboring 116 MHz. X-ray diffraction analyses reveal mixed-anion-induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho-free planes with favorable energetics for Li+ migration. Bond valence site energy analysis highlights preferred Li+ transport pathways, particularly in structural planes devoid of Ho3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li+ diffusion with Br- introduction into Li3HoCl6. Li-Ho electrostatic repulsions in the (001) plane presumably drive Li+ diffusion into the Ho-free (002) layer, enabling rapid intraplanar Li+ motion and exchange between the 2d and 4h sites. Li3-3 yHo1+ yCl6- xBrx also demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high-performance fast ion conductors for all-solid-state batteries.Localized atomistic disorder in halide-based solid electrolytes (SEs) can be leveraged to boost Li+ mobility. In this study, Li+ transport in structurally modified Li3HoCl6, via Br- introduction and Li+ deficiency, is explored. The optimized Li3-3 yHo1+ yCl6- xBrx achieves an ionic conductivity of 3.8 mS cm-1 at 25 °C, the highest reported for holmium halide materials. 6,7Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li+ motional rate neighboring 116 MHz. X-ray diffraction analyses reveal mixed-anion-induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho-free planes with favorable energetics for Li+ migration. Bond valence site energy analysis highlights preferred Li+ transport pathways, particularly in structural planes devoid of Ho3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li+ diffusion with Br- introduction into Li3HoCl6. Li-Ho electrostatic repulsions in the (001) plane presumab