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Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li7La3Zr2O12 Solid Electrolytes
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    Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li7La3Zr2O12 Solid Electrolytes
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    • Evgeniya Ilina*
      Evgeniya Ilina
      Institute of High-Temperature Electrochemistry of Ural Branch of RAS, Akademicheskaya Street, 20, Ekaterinburg 620990, Russia
      *Email: [email protected]. Phone: +7 343 362 31 81. Fax: +7 343 374 59 92.
    • Efim Lyalin
      Efim Lyalin
      Institute of High-Temperature Electrochemistry of Ural Branch of RAS, Akademicheskaya Street, 20, Ekaterinburg 620990, Russia
      More by Efim Lyalin
    • Maxim Vlasov
      Maxim Vlasov
      Institute of High-Temperature Electrochemistry of Ural Branch of RAS, Akademicheskaya Street, 20, Ekaterinburg 620990, Russia
      More by Maxim Vlasov
    • Artem Kabanov
      Artem Kabanov
      Samara Center for Theoretical Materials Science (SCTMS), Samara State Technical University, Molodogvardeyskaya Street, 244, Samara 443100, Russia
      P. N. Lebedev Physical Institute of the Russian Academy of Sciences, Novo-Sadovaya Street, 18, Samara 443011, Russia
    • Kirill Okhotnikov
      Kirill Okhotnikov
      Independent Site, Warsaw 02-206, Masovian Voivodeship, Poland
    • Elena Sherstobitova
      Elena Sherstobitova
      Institute of High-Temperature Electrochemistry of Ural Branch of RAS, Akademicheskaya Street, 20, Ekaterinburg 620990, Russia
    • Mirijam Zobel
      Mirijam Zobel
      Institute of Crystallography, RWTH Aachen University, Jägerstr. 17−19, Aachen 52066, Germany
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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2022, 5, 3, 2959–2967
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    https://doi.org/10.1021/acsaem.1c03632
    Published March 14, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Solid electrolytes with high values of lithium-ion conductivity are required for the creation of high-energy lithium and lithium-ion power sources, and compounds with a garnet structure based on Li7La3Zr2O12 (LLZO) are one of the candidate materials for this purpose. In the present work, solid electrolytes of the Li7–xLa3Zr2–xTaxO12 system with x = 0.0–2.0 were synthesized using the sol–gel method. According to X-ray diffraction analysis, all of the compounds with x ≥ 0.1 have the same cubic modification with the space group Iad. However, an increase in Ta concentration affects the short-range order crystal structure of these materials, resulting in higher local distortions, which was shown by pair distribution function (PDF) analysis. Particularly, the PDF data indicate an increase in the probability of Li ions to locally occupy not only two typical positions, Li1─96 h and Li2─24 d, but also a third one, Li3─48 g. The maximum value of lithium-ion conductivity in the studied system was observed for the Li6.4La3Zr1.4Ta0.6O12 compound (i.e., x = 0.6) and had the value of 1.4 × 10–4 S cm–1 at 25 °C. This is consistent with the results of density functional theory (DFT) modeling, which confirmed that a moderate Ta-doping (up to x < 1.0) is most suitable for enhancing Li diffusion in LLZO materials. A combination of DFT modeling, structural characterization of the short and average structures, and conductivity measurements in this work allowed getting insight into this important class of Li-conducting oxides and ideas on improving their properties.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.1c03632.

    • PDF fit parameters, additional PDF fitting plots, scheme of Li diffusion channels, and calculated Li migration maps (PDF)

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    Cited By

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    This article is cited by 6 publications.

    1. Cristina Lopez-Puga, Jincheng Du. Enhancing Lithium Ion Conduction in LLZO-Based Solid Electrolytes through Anion Doping for Advanced Energy Storage: Insights from Molecular Dynamics Simulations. Chemistry of Materials 2024, Article ASAP.
    2. Matthew S. Chambers, Jiadong Chen, Robert L. Sacci, Rebecca D. McAuliffe, Wenhao Sun, Gabriel M. Veith. Memory Effect on the Synthesis of Perovskite-Type Li-Ion Conductor LixLa2/3–x/3TiO3 (LLTO). Chemistry of Materials 2024, 36 (3) , 1197-1213. https://doi.org/10.1021/acs.chemmater.3c01928
    3. E. A. Il’ina, K. V. Druzhinin, T. A. Kuznetsova, M. E. Ozhiganov. Interface modification between Ta, Al-doped Li7La3Zr2O12 solid electrolyte and LiNi1/3Co1/3Mn1/3O2 cathode in all-solid-state batteries. Journal of Materials Science 2023, 58 (9) , 4070-4081. https://doi.org/10.1007/s10853-023-08268-y
    4. Zhiyuan Pang, Hongzhou Zhang, Lu Wang, Dawei Song, Xixi Shi, Yue Ma, Linglong Kong, Lianqi Zhang. Towards safe lithium-sulfur batteries from liquid-state electrolyte to solid-state electrolyte. Frontiers of Materials Science 2023, 17 (1) https://doi.org/10.1007/s11706-023-0630-3
    5. Yali Luo, Dingqian Dong, Jiacheng Zhou, Yuanjun Wang, Zihan Xue, Xue Jiang. Solid-state lithium-sulfur battery chemistries achieving excellent room-temperature cycle performance by high-quality Li7La3Zr2O12-based electrolyte. Journal of Alloys and Compounds 2023, 935 , 168112. https://doi.org/10.1016/j.jallcom.2022.168112
    6. Ling-Hsuan Huang, Chia-Chen Li. Liquid metallic Ga as sintering aid to promote the densification of garnet electrolytes for all-solid-state Li-ion batteries. Journal of Power Sources 2023, 556 , 232527. https://doi.org/10.1016/j.jpowsour.2022.232527

    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2022, 5, 3, 2959–2967
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsaem.1c03632
    Published March 14, 2022
    Copyright © 2022 American Chemical Society

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