Synthesis and electrochemical characterization of sulfur-doped Li3PO4 for all-solid-state battery applications: Original scientific paper

Hany El-Shinawi; Shady M. El-Dafrawy

doi:10.5599/jese.2498

Authors

Hany El-Shinawi Department of Chemistry, Faculty of Science, Mansoura University, Mansoura, 35516, Egypt https://orcid.org/0000-0002-4743-5576
Shady M. El-Dafrawy Department of Chemistry, Faculty of Science, Mansoura University, Mansoura, 35516, Egypt https://orcid.org/0009-0000-7297-4160

DOI:

https://doi.org/10.5599/jese.2498

Keywords:

Lithium ion battery, solid-state electrolyte, lithium superionic conductor, ionic conductivity, anion doping

Abstract

Isovalent and aliovalent cation-doping have been widely investigated to enhance ion transport in γ‑Li₃PO₄-type lithium superionic conductors (LISICONs). Anion doping, however, has been restricted to a full replacement of oxide ions by sulfide ions in some compounds (the so-called thio-LISICONs). The replacement of oxide ions by sulfide ions enhances both ion conductivity and deformability of the materials. Similar to other sulfide-type solid-electrolytes, thio-LISICONs, however, showed limited electrochemical stability against oxidation. In this report, a sonication-assisted liquid-phase synthesis approach was employed to achieve substantial sulfur‑oxygen mixing in γ-type Li₃PO₄. Sulfur-doped Li₃PO₄ possessed an ion conductivity four orders of magnitude higher than that of γ-Li₃PO₄, and a notably low activation energy of ion transport of 0.40(8) eV. Sulfur-oxygen mixing in sulfur-doped Li₃PO₄ enhanced electrochemical stability against oxidation (up to 4 V vs. Li⁺/Li) compared with sulfur-based Li₃PS₄. This study paves the way for developing mixed-anion phases in the γ-type Li₃PO₄ structure with enhanced electrochemical properties for all-solid-state battery applications.

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Synthesis and electrochemical characterization of sulfur-doped Li3PO4 for all-solid-state battery applications

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