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.
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