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Reducing the Defect Formation Energy by Aliovalent Sn(+IV) and Isovalent P(+V) Substitution in Li3SbS4 Promotes Li+ Transport

  • Bianca Helm
    Bianca Helm
    Institute of Inorganic and Analytical Chemistry, University of Muenster, Corrensstrasse 28/30, Muenster D-48149, Germany
    More by Bianca Helm
  • Kyra Strotmann
    Kyra Strotmann
    Institute of Inorganic and Analytical Chemistry, University of Muenster, Corrensstrasse 28/30, Muenster D-48149, Germany
  • Thorben Böger
    Thorben Böger
    Institute of Inorganic and Analytical Chemistry, University of Muenster, Corrensstrasse 28/30, Muenster D-48149, Germany
    International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), University of Muenster, Corrensstrasse 40, Muenster D-48149, Germany
  • Bibek Samanta
    Bibek Samanta
    International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), University of Muenster, Corrensstrasse 40, Muenster D-48149, Germany
    Institute of Physical Chemistry, University of Münster, Corrensstrasse 30, Münster D-48149, Germany
  • Ananya Banik
    Ananya Banik
    Research Institute for Sustainable Energy (RISE), TCG Centre for Research and Education in Science and Technology (TCG-CREST), Kolkata 700091, India
    More by Ananya Banik
  • Martin A. Lange
    Martin A. Lange
    Institute of Inorganic and Analytical Chemistry, University of Muenster, Corrensstrasse 28/30, Muenster D-48149, Germany
  • Yuheng Li
    Yuheng Li
    Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore
    Department of Materials Science and Engineering, National University of Singapore, Singapore 117575, Singapore
    More by Yuheng Li
  • Cheng Li
    Cheng Li
    Oak Ridge National Laboratory (ORNL), 1 Bethel Valley Road, Oak Ridge, Tennessee 37831-6473, United States
    More by Cheng Li
  • Michael Ryan Hansen
    Michael Ryan Hansen
    Institute of Physical Chemistry, University of Münster, Corrensstrasse 30, Münster D-48149, Germany
  • Pieremanuele Canepa
    Pieremanuele Canepa
    Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore
    Department of Materials Science and Engineering, National University of Singapore, Singapore 117575, Singapore
    Department of Electrical & Computer Engineering and Texas Center for Superconductivity, University of Houston, Houston, Texas 77204, United States
  • , and 
  • Wolfgang G. Zeier*
    Wolfgang G. Zeier
    Institute of Inorganic and Analytical Chemistry, University of Muenster, Corrensstrasse 28/30, Muenster D-48149, Germany
    Helmholtz Institute Muenster, FZ Jülich, Corrensstrasse 28/30, Muenster D-48149, Germany
    *Email: [email protected]
Cite this: ACS Appl. Energy Mater. 2024, 7, 5, 1735–1747
Publication Date (Web):February 29, 2024
https://doi.org/10.1021/acsaem.3c02652
Copyright © 2024 American Chemical Society

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    Abstract

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    The search for highly conducting Li+ solid electrolytes focuses on sulfide- and halide-based materials, where typically the strongly atomic disordered materials are the most promising. The atomic disorder corresponds to a flattened energy landscape having similar relative site energies for different Li+ positions facilitating motion. In addition, the highly disordered Li+ conductors have negligible defect formation energy as moving charges are readily available. This work investigates the isovalent Li3Sb1–xPxS4 (0 ≤ x ≤ 0.5) and the aliovalent Li3+xSb1–xSnxS4 (0 ≤ x ≤ 0.2) substitution series of thio-LISICON materials by using X-ray diffraction, high-resolution neutron diffraction, impedance spectroscopy, and defect calculations. The starting composition Li3SbS4 has a low ionic conductivity of ∼10–11 S·cm–1 and both substituents improve the ionic conductivity strongly by up to 4 orders of magnitude. On the one hand, in substituted Li3SbS4 structures, only minor structural changes are observed which cannot sufficiently explain the significant impact on the Li+ conductivity. On the other hand, the Li+ carrier density reveals a correlation to the activation energy and first-principles defect calculations, displaying significantly reduced defect formation energy upon substitution. Here, we show within two different substitution series that the defect formation energy plays a major role for ionic motion in this class of thio-LISICON materials.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.3c02652.

    • XRD data, neutron diffraction data, Rietveld refinement results, temperature-dependent impedance data, and pellet geometries and 6Li MAS NMR data on Li3.2Sn0.8Sb0.2S4 and Li4SnS4 (PDF)

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