Article From lithium to proton mobility in garnet electrolytes: an NMR and conductivity study of H 5.2 Li 1.3 La 3 Zr 1.5 Ta 0.5 O 12

Florian Stainer ORCID ; Junji Akimoto SAMURAI ORCID ; Yoshitaka Matsushita SAMURAI ORCID ; Kazutaka Mitsuishi SAMURAI ORCID ; Kazunori Takada SAMURAI ORCID ; H. Martin R. Wilkening ORCID

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Florian Stainer, Junji Akimoto, Yoshitaka Matsushita, Kazutaka Mitsuishi, Kazunori Takada, H. Martin R. Wilkening. From lithium to proton mobility in garnet electrolytes: an NMR and conductivity study of H 5.2 Li 1.3 La 3 Zr 1.5 Ta 0.5 O 12. Journal of Materials Chemistry A. 2026, 14 (31), 20491-20503. https://doi.org/10.1039/d5ta09970f

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(abstract)

Garnet-type oxides are among the most promising solid-state electrolytes owing to their high chemical stability and comparatively high lithium-ion conductivity. They may also provide a basis for proton conductors through Li+/H+ exchange. In a recent 1H and 7Li NMR study, we showed that minor proton incorporation in single-crystalline garnets exerts only a weak influence on Li-ion diffusion. Here, we investigate the polycrystalline hydrogarnet H5.2Li1.3La3Zr1.5Ta0.5O12 (HLZTO), obtained by aqueous Li+/H+ exchange from Li6.5La3Zr1.5Ta0.5O12 (LLZTO). The precursor, synthesised at the remarkably low temperature of 600 °C, exhibits a large surface area enabling an efficient exchange process. X-ray diffraction reveals a slight lattice expansion upon protonation, while 6Li high-resolution MAS NMR and Raman spectroscopy indicate a pronounced alteration of the local Li environment. Thermogravimetric analysis shows a 5.5 wt% loss between 200 and 600 °C, consistent with the release of H2O. The total ionic conductivity of LLZTO is constrained by poor interparticle contact, whereas in HLZTO it drops sharply upon heating as protons are removed. Variable-temperature 1H NMR relaxation reveals a diffusion-induced maximum between 125 and 180 °C, resulting in a self-diffusion coefficient D ≈ 1 × 10−15 m2 s−1 (ca. 150 °C). As seen by 7Li NMR, the remaining Li ions in HLZTO are almost immobile on the NMR time scale, revealing that proton motion dominates charge transport in HLZTO. While defects in LLZO promote localized motions, their healing appears to facilitate the establishment of long-range Li+ transport pathways.

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Keyword: garnet, proton conductor, NMR spectroscopy, conductivity

Date published: 2026-04-15

Publisher: Royal Society of Chemistry (RSC)

Journal:

  • Journal of Materials Chemistry A (ISSN: 20507488) vol. 14 issue. 31 p. 20491-20503

Funding:

  • Japan Society for the Promotion of Science JP24K08593
  • National Institute for Materials Science
  • Ministry of Education, Culture, Sports, Science and Technology

Manuscript type: Publisher's version (Version of record)

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First published URL: https://doi.org/10.1039/d5ta09970f

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Updated at: 2026-05-28 10:05:54 +0900

Published on MDR: 2026-05-28 12:38:37 +0900

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