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Crystalline precursor derived from Li3PS4 and ethylenediamine for ionic conductors

  • Invited Paper: Sol–gel and hybrid materials for dielectric, electronic, magnetic and ferroelectric applications
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Abstract

Liquid-phase syntheses of sulfide materials are attractive for the mass production of solid electrolytes for all-solid-state batteries. In liquid-phase synthesis, the precursor of the solid electrolyte is obtained. The precursors are important for producing electrolytes of the same quality because they decompose into electrolytes by heat treatment. However, only a few studies have focused on the formation mechanism and structure of precursors. This study proposes a formation mechanism for Li3PS4 during liquid-phase synthesis using ethylenediamine (EDA) as a solvent and clarifies the crystal structure of Li3PS4·NH2CH2CH2NH2 (Li3PS4·EDA). Raman spectroscopy and nuclear magnetic resonance revealed that intermediate P2S62− units were generated in the EDA solution. Crystal structure analysis of Li3PS4·EDA showed that the terminal nitrogen atom of EDA coordinates with two lithium atoms. Ionic conductivity of Li3PS4·EDA was 2.8 × 10−9 S cm−1 at 25 °C. The analysis of precursors of solid electrolytes provides insight into the behavior of solvent molecules as ligands in the synthesis of sulfide electrolytes.

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Highlights

  • β-Li3PS4 is prepared using a precursor obtained from Li3PS4 and ethylenediamine.

  • Intermediate P2S62− units are generated in the ethylenediamine solution.

  • Tetrahedra of PS4 and LiS4 form a framework in the precursor.

  • Ethylenediamine molecules coordinate to two lithium cations in the precursor.

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Funding

This work was supported by JSPS KAKENHI (Grant number 18H05255).

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University (presently, Osaka Metropolitan University), 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan

    Takuya Kimura, Akane Ito, Takumi Nakano, Chie Hotehama, Hiroe Kowada, Atsushi Sakuda, Masahiro Tatsumisago & Akitoshi Hayashi

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  1. Takuya Kimura
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  2. Akane Ito
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  3. Takumi Nakano
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  4. Chie Hotehama
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  7. Masahiro Tatsumisago
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  8. Akitoshi Hayashi
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Contributions

TK and AI carried out the synthesis, XRD measurement, Raman spectroscopy, and thermal analysis. TN and HK performed NMR. TK and CH conducted crystal structure analysis. AS, MT, and AH supervised the research. TK wrote the manuscript and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Akitoshi Hayashi.

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Kimura, T., Ito, A., Nakano, T. et al. Crystalline precursor derived from Li3PS4 and ethylenediamine for ionic conductors. J Sol-Gel Sci Technol 104, 627–634 (2022). https://doi.org/10.1007/s10971-022-05824-x

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