Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries

Ji Eun Lee; Kern Ho Park; Jin Chul Kim; Tae Ung Wi; A. Reum Ha; Yong Bae Song; Dae Yang Oh; Jehoon Woo; Seong Hyeon Kweon; Su Jeong Yeom; Woosuk Cho; Kyung Su Kim; Hyun Wook Lee; Sang Kyu Kwak; Yoon Seok Jung

doi:10.1002/adma.202200083

Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries

Ji Eun Lee, Kern Ho Park, Jin Chul Kim, Tae Ung Wi, A. Reum Ha, Yong Bae Song, Dae Yang Oh, Jehoon Woo, Seong Hyeon Kweon, Su Jeong Yeom, Woosuk Cho, Kyung Su Kim, Hyun Wook Lee, Sang Kyu Kwak, Yoon Seok Jung

Department of Chemical and Biomolecular Engineering

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

Abstract

The wet-chemical processability of sulfide solid electrolytes (SEs) provides intriguing opportunities for all-solid-state batteries. Thus far, sulfide SEs are wet-prepared either from solid precursors suspended in solvents (suspension synthesis) or from homogeneous solutions using SEs (solution process) with restricted composition spaces. Here, a universal solution synthesis method for preparing sulfide SEs from precursors, not only Li₂S, P₂S₅, LiCl, and Na₂S, but also metal sulfides (e.g., GeS₂ and SnS₂), fully dissolved in an alkahest: a mixture solvent of 1,2-ethylenediamine (EDA) and 1,2-ethanedithiol (EDT) (or ethanethiol). Raman spectroscopy and theoretical calculations reveal that the exceptional dissolving power of EDA–EDT toward GeS₂ is due to the nucleophilicity of the thiolate anions that is strong enough to dissociate the Ge-S bonds. Solution-synthesized Li₁₀GeP₂S₁₂, Li₆PS₅Cl, and Na₁₁Sn₂PS₁₂ exhibit high ionic conductivities (0.74, 1.3, and 0.10 mS cm⁻¹ at 30 °C, respectively), and their application for all-solid-state batteries is successfully demonstrated.

Original language	English
Article number	2200083
Journal	Advanced Materials
Volume	34
Issue number	16
DOIs	https://doi.org/10.1002/adma.202200083
Publication status	Published - 2022 Apr 21

Bibliographical note

Funding Information:
J.E.L., K.‐H.P., and J.C.K. contributed equally to this work. This work was supported by the Technology Development Program to Solve Climate Changes and by the Basic Science Research Program of the National Research Foundation (NRF) funded by the Ministry of Science & ICT (Grant No. NRF‐2017M1A2A2044501), the Materials and Components Technology Development Program of MOTIE/KEIT (Grant Nos. 10076731 and 20007045), and by the Yonsei University Research Fund of 2021 (2021‐22‐0326). H.‐W.L. acknowledges support from the 2022 Research Fund (1.220022.01) of UNIST and the Individual Basic Science and Engineering Research Program (NRF‐2019R1C1C1009324). The computational resources were provided by UNIST‐HPC and KISTI (KSC‐2021‐CRE‐0184).

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Materials Science(all)
Mechanics of Materials
Mechanical Engineering

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@article{f62bda25c5fb46c1b82a0ce389829636,

title = "Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries",

abstract = "The wet-chemical processability of sulfide solid electrolytes (SEs) provides intriguing opportunities for all-solid-state batteries. Thus far, sulfide SEs are wet-prepared either from solid precursors suspended in solvents (suspension synthesis) or from homogeneous solutions using SEs (solution process) with restricted composition spaces. Here, a universal solution synthesis method for preparing sulfide SEs from precursors, not only Li2S, P2S5, LiCl, and Na2S, but also metal sulfides (e.g., GeS2 and SnS2), fully dissolved in an alkahest: a mixture solvent of 1,2-ethylenediamine (EDA) and 1,2-ethanedithiol (EDT) (or ethanethiol). Raman spectroscopy and theoretical calculations reveal that the exceptional dissolving power of EDA–EDT toward GeS2 is due to the nucleophilicity of the thiolate anions that is strong enough to dissociate the Ge-S bonds. Solution-synthesized Li10GeP2S12, Li6PS5Cl, and Na11Sn2PS12 exhibit high ionic conductivities (0.74, 1.3, and 0.10 mS cm−1 at 30 °C, respectively), and their application for all-solid-state batteries is successfully demonstrated.",

author = "Lee, {Ji Eun} and Park, {Kern Ho} and Kim, {Jin Chul} and Wi, {Tae Ung} and Ha, {A. Reum} and Song, {Yong Bae} and Oh, {Dae Yang} and Jehoon Woo and Kweon, {Seong Hyeon} and Yeom, {Su Jeong} and Woosuk Cho and Kim, {Kyung Su} and Lee, {Hyun Wook} and Kwak, {Sang Kyu} and Jung, {Yoon Seok}",

note = "Funding Information: J.E.L., K.‐H.P., and J.C.K. contributed equally to this work. This work was supported by the Technology Development Program to Solve Climate Changes and by the Basic Science Research Program of the National Research Foundation (NRF) funded by the Ministry of Science & ICT (Grant No. NRF‐2017M1A2A2044501), the Materials and Components Technology Development Program of MOTIE/KEIT (Grant Nos. 10076731 and 20007045), and by the Yonsei University Research Fund of 2021 (2021‐22‐0326). H.‐W.L. acknowledges support from the 2022 Research Fund (1.220022.01) of UNIST and the Individual Basic Science and Engineering Research Program (NRF‐2019R1C1C1009324). The computational resources were provided by UNIST‐HPC and KISTI (KSC‐2021‐CRE‐0184). Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = apr,

day = "21",

doi = "10.1002/adma.202200083",

language = "English",

volume = "34",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "Wiley-VCH Verlag",

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T1 - Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries

AU - Lee, Ji Eun

AU - Park, Kern Ho

AU - Kim, Jin Chul

AU - Wi, Tae Ung

AU - Ha, A. Reum

AU - Song, Yong Bae

AU - Oh, Dae Yang

AU - Woo, Jehoon

AU - Kweon, Seong Hyeon

AU - Yeom, Su Jeong

AU - Cho, Woosuk

AU - Kim, Kyung Su

AU - Lee, Hyun Wook

AU - Kwak, Sang Kyu

AU - Jung, Yoon Seok

N1 - Funding Information: J.E.L., K.‐H.P., and J.C.K. contributed equally to this work. This work was supported by the Technology Development Program to Solve Climate Changes and by the Basic Science Research Program of the National Research Foundation (NRF) funded by the Ministry of Science & ICT (Grant No. NRF‐2017M1A2A2044501), the Materials and Components Technology Development Program of MOTIE/KEIT (Grant Nos. 10076731 and 20007045), and by the Yonsei University Research Fund of 2021 (2021‐22‐0326). H.‐W.L. acknowledges support from the 2022 Research Fund (1.220022.01) of UNIST and the Individual Basic Science and Engineering Research Program (NRF‐2019R1C1C1009324). The computational resources were provided by UNIST‐HPC and KISTI (KSC‐2021‐CRE‐0184). Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022/4/21

Y1 - 2022/4/21

N2 - The wet-chemical processability of sulfide solid electrolytes (SEs) provides intriguing opportunities for all-solid-state batteries. Thus far, sulfide SEs are wet-prepared either from solid precursors suspended in solvents (suspension synthesis) or from homogeneous solutions using SEs (solution process) with restricted composition spaces. Here, a universal solution synthesis method for preparing sulfide SEs from precursors, not only Li2S, P2S5, LiCl, and Na2S, but also metal sulfides (e.g., GeS2 and SnS2), fully dissolved in an alkahest: a mixture solvent of 1,2-ethylenediamine (EDA) and 1,2-ethanedithiol (EDT) (or ethanethiol). Raman spectroscopy and theoretical calculations reveal that the exceptional dissolving power of EDA–EDT toward GeS2 is due to the nucleophilicity of the thiolate anions that is strong enough to dissociate the Ge-S bonds. Solution-synthesized Li10GeP2S12, Li6PS5Cl, and Na11Sn2PS12 exhibit high ionic conductivities (0.74, 1.3, and 0.10 mS cm−1 at 30 °C, respectively), and their application for all-solid-state batteries is successfully demonstrated.

AB - The wet-chemical processability of sulfide solid electrolytes (SEs) provides intriguing opportunities for all-solid-state batteries. Thus far, sulfide SEs are wet-prepared either from solid precursors suspended in solvents (suspension synthesis) or from homogeneous solutions using SEs (solution process) with restricted composition spaces. Here, a universal solution synthesis method for preparing sulfide SEs from precursors, not only Li2S, P2S5, LiCl, and Na2S, but also metal sulfides (e.g., GeS2 and SnS2), fully dissolved in an alkahest: a mixture solvent of 1,2-ethylenediamine (EDA) and 1,2-ethanedithiol (EDT) (or ethanethiol). Raman spectroscopy and theoretical calculations reveal that the exceptional dissolving power of EDA–EDT toward GeS2 is due to the nucleophilicity of the thiolate anions that is strong enough to dissociate the Ge-S bonds. Solution-synthesized Li10GeP2S12, Li6PS5Cl, and Na11Sn2PS12 exhibit high ionic conductivities (0.74, 1.3, and 0.10 mS cm−1 at 30 °C, respectively), and their application for all-solid-state batteries is successfully demonstrated.

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DO - 10.1002/adma.202200083

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Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries

Abstract

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