DataVXACS Applied Energy MaterialsPaper
journal article·2024-03-11

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

Bianca Helm, Kyra Strotmann, Thorben Böger, Bibek Samanta, Ananya Banik, Martin A. Lange, Yuheng Li, Cheng Li, Michael Ryan Hansen, Pieremanuele Canepa, Wolfgang G. Zeier

ACS Applied Energy Materials· Volume 7· Issue 5
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Source abstract

Abstract

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 Li 3 Sb 1– x P x S 4 (0 ≤ x ≤ 0.5) and the aliovalent Li 3+ x Sb 1– x Sn x S 4 (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 Li 3 SbS 4 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 Li 3 SbS 4 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.
Source: openalex_inverted_index · Quality: baseline

Research context

Energy storage

OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Inorganic Chemistry and Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

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

Institute of Physical Chemistry, University of Münster, Corrensstrasse 30, Münster D-48149, Germany

Research Institute for Sustainable Energy (RISE), TCG Centre for Research and Education in Science and Technology (TCG-CREST), Kolkata 700091, India

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

Oak Ridge National Laboratory (ORNL), 1 Bethel Valley Road, Oak Ridge, Tennessee 37831-6473, United States

Department of Electrical & Computer Engineering and Texas Center for Superconductivity, University of Houston, Houston, Texas 77204, United States

Helmholtz Institute Muenster, FZ Jülich, Corrensstrasse 28/30, Muenster D-48149, Germany

Funding

Bundesministerium f?r Bildung und Forschung · Welch Foundation · Deutsche Forschungsgemeinschaft · National Research Foundation Singapore

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