• Accepted Paper

Non-Arrhenius lithium diffusion with temperature-independent Haven ratio in garnet-type Li6.5La3Zr1.5Ta0.5O12 single crystals

Kaori Sugii, Gen Hasegawa, Kunimitsu Kataoka, Kenjiro Hashi, Junji Akimoto, Kazunori Takada, and Naoaki Kuwata

PRX Energy - Accepted 4 September, 2026

DOI: https://doi.org/10.1103/zld4-bjxp

Abstract

Lithium-ion dynamics of garnet-type Li6.5La3Zr1.5Ta0.5O12 single crystals were investigated using pulsed field gradient (PFG) NMR and impedance spectroscopy over a wide temperature range up to 700 K. The diffusion coefficient measured by PFG-NMR exhibits non-Arrhenius behavior at elevated temperatures (>400 K). The conductivity diffusion coefficient is consistently higher than the PFG-NMR diffusion coefficient across the entire temperature range, with a Haven ratio of 0.3–0.4, indicating that the motion of mobile Li+ ions is correlated. Remarkably, the Haven ratio exhibits little temperature dependence despite the non-Arrhenius behavior, representing the first experimental observation in garnet-type electrolytes and consistent with the molecular dynamics simulations. This indicates that ion–ion correlations remain essentially unchanged over a wide temperature range. Combined with the local Li+ ion dynamics obtained from spin-lattice relaxation analysis, these results suggest that long-range diffusion is suppressed at low temperatures due to short-range ordering of Li+ ions.

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