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Lithium-site substituted argyrodite-type Li6PS5I solid electrolytes with enhanced ionic conduction for all-solid-state batteries

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Abstract

Argyrodites, Li6PS5X (X=Cl, Br, I), have piqued the interest of researchers by offering promising lithium ionic conductivity for their application in all-solid-state batteries (ASSBs). However, other than Li6PS5Cl (651Cl) and Li6PS5Br (651Br), Li6PS5I (651I) shows poor ionic conductivity (10−7 S cm−1 at 298 K). Herein, we present Al-doped 651I with I−/S2− site disordering to lower activation energy (Ea) and improve ionic conductivity. They formed argyrodite-type solid solutions with a composition of (Li6−3xAlx)PS5I in 0⩽x⩽0.10, and structural analysis revealed that Al3+ is located at Li sites. Also, the Al-doped samples contained anion I−/S2− site disorders in the crystal structures and smaller lattice parameters than the non-doped samples. Impedance spectroscopy measurements indicated that Al-doping reduced the ionic diffusion barrier, Ea, and increased the ionic conductivity to 10−5 S cm−1; the (Li5.7Al0.1)PS5I had the highest ionic conductivity in the studied system, at 2.6×10−5 S cm−1. In a lab-scale ASSB, with (Li5.7Al0.1)PS5I functioned as a solid electrolyte, demonstrating the characteristics of a pure ionic conductor with negligible electronic conductivity. The evaluated ionic conduction is due to decreased Li+ content and I−/S2− disorder formation. Li-site cation doping enables an in-depth understanding of the structure and provides an additional approach to designing better-performing SEs in the argyrodite system.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Huanggang Normal University, Huanggang, 438000, China

    Ling Gao, YuLin Xie, Yan Tong, JiaLe You, HuiPing Wei, XiangXiang Yu, SiQi Xu, Yi Zhang & GuoWei Zhao

  2. State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai, 200245, China

    Miao Xu

  3. Shanghai Enpower Technology Co., Ltd., Shanghai, 201802, China

    Yong Che

  4. Beijing Enpower Technology Co., Ltd., Beijing, 102628, China

    Yong Che

  5. Department of Chemistry, School of Science, Shanghai University, Shanghai, 200444, China

    Ya Tang

  6. Research Center for All-Solid-State Battery, Institute of Innovation Research, Tokyo Institute of Technology, Yokohama, 226-8502, Japan

    Kota Suzuki & Ryoji Kanno

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  1. Ling Gao
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  2. YuLin Xie
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  3. Yan Tong
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  11. Ya Tang
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Corresponding authors

Correspondence to Miao Xu or GuoWei Zhao.

Additional information

This work was supported by the Hundred-Talent Project of Hubei Province, China (Grant No. 2021HG01), the Huanggang Young Talent, China (Grant No. HRZF2022-5), the Pearl Scholars Research Programs (Grant Nos. P20190218, P20190219), and Young Scholars Start-up Research Programs of Huanggang Normal University, China (Grant Nos. Y20190218, Y20190219). This work was also partly conducted in collaboration with Shanghai Enpower Technology Co., Ltd. and Beijing Enpower Technology Co., Ltd.

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Lithium-site substituted Argyrodite-type Li6PS5I Solid Electrolytes with Enhanced Ionic Conduction for All-Solid-State Batteries

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Gao, L., Xie, Y., Tong, Y. et al. Lithium-site substituted argyrodite-type Li6PS5I solid electrolytes with enhanced ionic conduction for all-solid-state batteries. Sci. China Technol. Sci. 66, 2059–2068 (2023). https://doi.org/10.1007/s11431-022-2365-8

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