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Competing Effects in the Hydration Mechanism of a Garnet-Type Li7La3Zr2O12 Electrolyte

  • Yulia Arinicheva
    Yulia Arinicheva
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
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    Orcidhttps://orcid.org/0000-0003-0629-3484
  • , 
  • Xin Guo
    Xin Guo
    Eyring Materials Center, Arizona State University, P.O. Box 878301, Tempe, Arizona 85287-8301, United States
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  • , 
  • Marie-Theres Gerhards
    Marie-Theres Gerhards
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
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  • Frank Tietz
    Frank Tietz
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
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  • , 
  • Dina Fattakhova-Rohlfing
    Dina Fattakhova-Rohlfing
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
    Helmholtz Institute Münster: Ionics in Energy Storage (IEK-12), Forschungszentrum Jülich GmbH, Corrensstrasse 46, 48149 Münster, Germany
    Faculty of Engineering, Center for Nanointegration Duisburg-Essen, Universität Duisburg-Essen, Lotharstrasse 1, 47057 Duisburg, Germany
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  • , 
  • Martin Finsterbusch*
    Martin Finsterbusch
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
    Helmholtz Institute Münster: Ionics in Energy Storage (IEK-12), Forschungszentrum Jülich GmbH, Corrensstrasse 46, 48149 Münster, Germany
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0001-7027-7636
  • , 
  • Alexandra Navrotsky
    Alexandra Navrotsky
    Navrotsky Eyring Center for Materials of the Universe, Arizona State University, Tempe, Arizona 85281, United States
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    Orcidhttps://orcid.org/0000-0002-3260-0364
  • , and 
  • Olivier Guillon
    Olivier Guillon
    Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-1): Materials Synthesis and Processing, 52425 Jülich, Germany
    Jülich Aachen Research Alliance, JARA-Energy, 52425 Jülich, Germany
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Cite this: Chem. Mater. 2022, 34, 4, 1473–1480
Publication Date (Web):February 8, 2022
https://doi.org/10.1021/acs.chemmater.1c02581
Copyright © 2022 American Chemical Society
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    Abstract

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    Li-ion conducting oxides (Li7La3Zr2O12, LLZO) with a cubic garnet-type structure are among the most promising candidates to be used as solid electrolytes in all-solid-state Li batteries. However, the environmental instability of the electrolyte, induced by interaction between the material and gas molecules commonly found in air, namely, water and carbon dioxide, poses challenges for its manufacture and application. Herein, a combined experimental kinetic and thermodynamic study was performed as a function of temperature to clarify the mechanism of hydration of a garnet-type LLZO electrolyte in moist air. It was found that the kinetics of LLZO hydration is diffusion-limited and the hydration mechanism at room temperature and at higher temperatures differs. The hydration of LLZO increases up to 200 °C. Above this temperature, stagnation of water uptake is observed due to the onset of a competing dehydration process. The dehydration of LLZO takes place up to 400 °C. The partial pressure of water significantly affects the extent of hydration. Expanding this combined kinetic and thermodynamic approach to LLZO materials with a variety of chemical compositions and morphologies would allow prediction of their reactivity in a humid atmosphere and adjustment of the processing conditions accordingly to meet the requirements of technological applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.1c02581.

    • Powder X-ray diffraction patterns of LLZO pellets (Figure S1), TG-DTA curves of LLZO powder synthesized in air and heated in an Ar atmosphere at a rate of 5 °C min–1 (Figure S2), TG-DTA curves of degassing of LLZO powder at 750 °C in an Ar atmosphere (heating/cooling rate of 5 °C min–1) and subsequent isothermal heating at 150 °C in the gas mixture of water vapor and argon (Figure S3), TG curves of degassing of LLZO powder at 750 °C in an Ar atmosphere (heating/cooling rate of 5 °C min–1) and subsequent isothermal heating at 200 °C in the gas mixture of water vapor and argon repeated three times (Figure S4), Arrhenius plot of the initial reaction rate of LLZO with water vapor as a function of inverse temperature (Figure S5), and crystal structure of cubic Li6.5La3Zr1.5Ta0.5O12 (COD ID 1545083) (Figure S6) (PDF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 5 publications.

    1. Sundeep Vema, Farheen N. Sayed, Supreeth Nagendran, Burcu Karagoz, Christian Sternemann, Michael Paulus, Georg Held, Clare P. Grey. Understanding the Surface Regeneration and Reactivity of Garnet Solid-State Electrolytes. ACS Energy Letters 2023, 8 (8) , 3476-3484. https://doi.org/10.1021/acsenergylett.3c01042
    2. Nina Hoinkis, Jörg Schuhmacher, Sebastian Leukel, Christoph Loho, Andreas Roters, Felix H. Richter, Jürgen Janek. Particle Size-Dependent Degradation Kinetics of Garnet-Type Li6.5La3Zr1.5Ta0.5O12 Solid Electrolyte Powders in Ambient Air. The Journal of Physical Chemistry C 2023, 127 (17) , 8320-8331. https://doi.org/10.1021/acs.jpcc.3c01027
    3. Masanobu Nakayama, Takuya Horie, Ryosuke Natsume, Shogo Hashimura, Naoto Tanibata, Hayami Takeda, Hirotaka Maeda, Masashi Kotobuki. Reaction Kinetics of Carbonation at the Surface of Garnet-Type Li7La3Zr2O12 as Solid Electrolytes for All-Solid-State Li Ion Batteries. The Journal of Physical Chemistry C 2023, 127 (16) , 7595-7601. https://doi.org/10.1021/acs.jpcc.2c08588
    4. Xiaoxue Zhao, Chao Wang, Hong Liu, Yuhao Liang, Li‐Zhen Fan. A Review of Polymer‐based Solid‐State Electrolytes for Lithium‐Metal Batteries: Structure, Kinetic, Interface Stability, and Application. Batteries & Supercaps 2023, 118 https://doi.org/10.1002/batt.202200502
    5. Alexandra C. Moy, Grit Häuschen, Dina Fattakhova-Rohlfing, Jeffrey B. Wolfenstine, Martin Finsterbusch, Jeff Sakamoto. The effects of aluminum concentration on the microstructural and electrochemical properties of lithium lanthanum zirconium oxide. Journal of Materials Chemistry A 2022, 10 (41) , 21955-21972. https://doi.org/10.1039/D2TA03676B
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