Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

Park, Dongsu; Kim, Kwangnam; Chun, Gin Hyung; Wood, Brandon C.; Shim, Joon Hyung; Yu, Seungho

doi:10.1039/d1ta07050a

Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

Journal Article · Thu Sep 16 00:00:00 EDT 2021 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d1ta07050a· OSTI ID:1844069

Park, Dongsu ^[1]; Kim, Kwangnam ^[2]; Chun, Gin Hyung ^[1]; Wood, Brandon C. ^[2]; ^[3]; ^[4]

Korea Institute of Science and Technology, Seoul (Korea, Republic of); Korea Univ., Seoul, (Korea, Republic of)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Korea Univ., Seoul, (Korea, Republic of)
Korea Institute of Science and Technology, Seoul (Korea, Republic of); Korea Univ. of Science and Technology, Seoul, (Korea, Republic of)

All-solid-state sodium-ion batteries have attracted increasing attention owing to the low cost of sodium and the enhanced safety compared to conventional Li-ion batteries. Recently, halides have been considered as promising solid electrolytes (SEs) due to their favorable combination of high ionic conductivity and chemical stability against high-voltage cathode materials. Although a wide variety of lithium chloride SEs, Li₃MCl₆, have been developed for high-voltage all-solid-state batteries, only a limited number of sodium chloride SEs have been reported. This study aims to offer a material design insight for the development of sodium chloride SEs through systematic assessment of the phase stability, electrochemical stability, and transport properties of novel Na₃MCl₆ SEs. Structural calculations indicate that Na₃MCl₆ exhibits trigonal $$P\bar{3}$$1c, monoclinic P2₁/n, and trigonal $$R\bar{3}$$ phases, and the stable phase of Na₃MCl₆ is dependent on the type and ionic radius of M. Na₃MCl₆ typically exhibits a high oxidation potential, demonstrating good electrochemical stability against cathodes. The bond-valence site energy and ab initio molecular dynamics calculations revealed that Na₃MCl₆ with P2₁/n and $$R\bar{3}$$ phases showed low ionic conductivity, while the $$P\bar{3}$$1c phase slightly improved the ionic conductivity of Na₃MCl₆. The formation of Na vacancies by aliovalent substitution considerably increased the ionic conductivity up to four orders of magnitude for pristine Na₃MCl₆, exhibiting ~10^–5 S cm^–1 for trigonal $$P\bar{3}$$1c and $$R\bar{3}$$ phases. The formation of defects could further enhance the ionic conductivity of Na₃MCl₆, and the optimization of defect type and ratio can be helpful in developing superionic Na chloride SEs. The material design of Na₃MCl₆ in this study will provide fundamental guidelines for the development of novel sodium halide SEs for all-solid-state sodium-ion batteries.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: Korea Institute of Science and Technology; Ministry of Trade, Industry & Energy of Korea; National Research Foundation of Korea (NRF); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1844069

Alternate ID(s):: OSTI ID: 1824865

Report Number(s):: LLNL-JRNL--825812; 1039236

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 40 Vol. 9; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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