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Simultaneously Improved Cubic Phase Stability and Li-Ion Conductivity in Garnet-Type Solid Electrolytes Enabled by Controlling the Al Occupation Sites
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    Energy, Environmental, and Catalysis Applications

    Simultaneously Improved Cubic Phase Stability and Li-Ion Conductivity in Garnet-Type Solid Electrolytes Enabled by Controlling the Al Occupation Sites
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    • Abin Kim
      Abin Kim
      Department of Materials Science and Engineering (MSE), Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, Republic of Korea
      More by Abin Kim
    • Joo-Hee Kang
      Joo-Hee Kang
      Department of Materials Analysis, Korea Institute of Materials Science, Changwon, Gyeongnam 51508, Republic of Korea
      More by Joo-Hee Kang
    • Kyung Song
      Kyung Song
      Department of Materials Analysis, Korea Institute of Materials Science, Changwon, Gyeongnam 51508, Republic of Korea
      More by Kyung Song
    • Byoungwoo Kang*
      Byoungwoo Kang
      Department of Materials Science and Engineering (MSE), Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, Republic of Korea
      *Email: [email protected]
    Other Access OptionsSupporting Information (1)

    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2022, 14, 10, 12331–12339
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    https://doi.org/10.1021/acsami.2c01361
    Published February 25, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Here, we, for the first time, report on the simultaneous enhancement in cubic phase stability and Li-ion conductivity of garnet-type solid electrolytes (SEs) by adding excess Li/Al. The excess Al/Li creates very large grains of up to 170 μm via the segregation of Al at the grain boundaries and enables preferential Al occupation at 96h sites over 24d sites, a behavior contrary to previous observations. The resulting SE shows improved Li-ion conductivity due to the large grain size and less blocking Li pathway caused by different preferential Al occupation. Surprisingly, it is observed that the cubic phase of the garnet-type SE is transformed to the tetragonal phase on the surface and in the bulk under the applied voltage, and the preferential Al occupation enables its cubic phase stability. Under battery operating conditions, the LLZO SE with excess Li/Al can maintain high ionic conductivity due to the cubic phase stability and large grain size. We clearly demonstrate that the cubic phase stability and ionic conductivity of LLZO can be simultaneously improved by excess Li/Al without any post-treatments. The findings and understanding will provide new insights into practical use of the garnet-type SEs for advanced all solid-state batteries.

    Copyright © 2022 American Chemical Society

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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/acsami.2c01361.

    • Raw data of Arrhenius plots at various temperatures of E-LLZO and B-LLZO and XRD refinement of the two samples (E-LLZO and B-LLZO) after the dielectric test (PDF)

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    Cited By

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    This article is cited by 6 publications.

    1. Abin Kim, Kyung Song, Maxim Avdeev, Byoungwoo Kang. High Energy Density Ultra-thin Li Metal Solid-State Battery Enabled by a Li2CO3-Proof Garnet-Type Solid Electrolyte. ACS Energy Letters 2024, 9 (5) , 1976-1983. https://doi.org/10.1021/acsenergylett.4c00217
    2. Dexin Zhang, Yiwei You, Fulun Wu, Xinrui Cao, Tie-Yu Lü, Yang Sun, Zi-Zhong Zhu, Shunqing Wu. Exploring the Relationship between Composition and Li-Ion Conductivity in the Amorphous Li–La–Zr–O System. ACS Materials Letters 2024, 6 (5) , 1849-1855. https://doi.org/10.1021/acsmaterialslett.3c01558
    3. Meng Liu, Wenhao Xie, Bin Li, Yibo Wang, Guangqi Li, Songtong Zhang, Yuehua Wen, Jingyi Qiu, Junhong Chen, Pengcheng Zhao. Garnet Li7La3Zr2O12-Based Solid-State Lithium Batteries Achieved by In Situ Thermally Polymerized Gel Polymer Electrolyte. ACS Applied Materials & Interfaces 2022, 14 (38) , 43116-43126. https://doi.org/10.1021/acsami.2c09028
    4. Z. Zhang, X. Wang, X. Li, J. Zhao, G. Liu, W. Yu, X. Dong, J. Wang. Review on composite solid electrolytes for solid-state lithium-ion batteries. Materials Today Sustainability 2023, 21 , 100316. https://doi.org/10.1016/j.mtsust.2023.100316
    5. Junlong Liu, Tao Wang, Jinjian Yu, Shuyang Li, Hong Ma, Xiaolong Liu. Review of the Developments and Difficulties in Inorganic Solid-State Electrolytes. Materials 2023, 16 (6) , 2510. https://doi.org/10.3390/ma16062510
    6. Meng Liu, Haiyang Chen, Songtong Zhang, Guangqi Li, Bin Li, Yuehua Wen, Jingyi Qiu, Junhong Chen, Pengcheng Zhao. Key factors of the self-consolidation mechanism for sintering Li7La3Zr2O12 solid electrolytes. Journal of Power Sources 2023, 556 , 232447. https://doi.org/10.1016/j.jpowsour.2022.232447

    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2022, 14, 10, 12331–12339
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.2c01361
    Published February 25, 2022
    Copyright © 2022 American Chemical Society

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