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

Title: 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.

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

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

Grant/Contract Number:: AC52-07NA27344; 2017M1A2A2044482; 20012318; 2E30992

OSTI ID:: 1844069

Alternate ID(s):: OSTI ID: 1824865

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

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

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries Park, Kern-Ho; Kaup, Kavish; Assoud, Abdeljalil ACS Energy Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsenergylett.9b02599	journal	January 2020
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Heat treatment protocol for modulating ionic conductivity via structural evolution of Li3-xYb1-xMxCl6 (M = Hf4+, Zr4+) new halide superionic conductors for all-solid-state batteries Park, Juhyoun; Han, Daseul; Kwak, Hiram Chemical Engineering Journal, Vol. 425 https://doi.org/10.1016/j.cej.2021.130630	journal	December 2021
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
A new halospinel superionic conductor for high-voltage all solid state lithium batteries Zhou, Laidong; Kwok, Chun Yuen; Shyamsunder, Abhinandan Energy & Environmental Science, Vol. 13, Issue 7 https://doi.org/10.1039/D0EE01017K	journal	January 2020
Na3GdCl6: Einkristalle der Tieftemperaturform bei der metallothermischen Reduktion von GdCl3 mit Na Meyer, Gerd Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 517, Issue 10 https://doi.org/10.1002/zaac.19845171019	journal	October 1984
Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries Li, Xiaona; Liang, Jianwen; Yang, Xiaofei Energy & Environmental Science, Vol. 13, Issue 5 https://doi.org/10.1039/C9EE03828K	journal	January 2020
Sodium Plating from Na‐β″‐Alumina Ceramics at Room Temperature, Paving the Way for Fast‐Charging All‐Solid‐State Batteries Bay, Marie‐Claude; Wang, Michael; Grissa, Rabeb Advanced Energy Materials, Vol. 10, Issue 3 https://doi.org/10.1002/aenm.201902899	journal	December 2019
Influence of Lattice Dynamics on Na ⁺ Transport in the Solid Electrolyte Na ₃ PS _{4– x} Se _x Krauskopf, Thorben; Pompe, Constantin; Kraft, Marvin A. Chemistry of Materials, Vol. 29, Issue 20 https://doi.org/10.1021/acs.chemmater.7b03474	journal	October 2017
Predicting Charge Transfer Stability between Sulfide Solid Electrolytes and Li Metal Anodes Park, Haesun; Yu, Seungho; Siegel, Donald J. ACS Energy Letters, Vol. 6, Issue 1 https://doi.org/10.1021/acsenergylett.0c02372	journal	December 2020
A wide-ranging review on Nasicon type materials Anantharamulu, N.; Koteswara Rao, K.; Rambabu, G. Journal of Materials Science, Vol. 46, Issue 9 https://doi.org/10.1007/s10853-011-5302-5	journal	February 2011
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
A sodium-ion sulfide solid electrolyte with unprecedented conductivity at room temperature Hayashi, A.; Masuzawa, N.; Yubuchi, S. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13178-2	journal	November 2019
Air-stable Li ₃ InCl ₆ electrolyte with high voltage compatibility for all-solid-state batteries Li, Xiaona; Liang, Jianwen; Luo, Jing Energy & Environmental Science, Vol. 12, Issue 9 https://doi.org/10.1039/C9EE02311A	journal	January 2019
Material Design Strategy for Halide Solid Electrolytes Li ₃ MX ₆ (X = Cl, Br, and I) for All-Solid-State High-Voltage Li-Ion Batteries Kim, Kwangnam; Park, Dongsu; Jung, Hun-Gi Chemistry of Materials, Vol. 33, Issue 10 https://doi.org/10.1021/acs.chemmater.1c00555	journal	May 2021
Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte Li, Xiaona; Liang, Jianwen; Chen, Ning Angewandte Chemie International Edition, Vol. 58, Issue 46 https://doi.org/10.1002/anie.201909805	journal	November 2019
Na ₃ SbS ₄ : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries Banerjee, Abhik; Park, Kern Ho; Heo, Jongwook W. Angewandte Chemie International Edition, Vol. 55, Issue 33 https://doi.org/10.1002/anie.201604158	journal	July 2016
Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li ₃ MCl ₆ (M = Y, Er) Superionic Conductors Schlem, Roman; Muy, Sokseiha; Prinz, Nils Advanced Energy Materials, Vol. 10, Issue 6 https://doi.org/10.1002/aenm.201903719	journal	December 2019
Structural change of Li2S–P2S5 sulfide solid electrolytes in the atmosphere Muramatsu, Hiromasa; Hayashi, Akitoshi; Ohtomo, Takamasa Solid State Ionics, Vol. 182, Issue 1 https://doi.org/10.1016/j.ssi.2010.10.013	journal	February 2011
Superionic Si-Substituted Lithium Argyrodite Sulfide Electrolyte Li _{6+ x} Sb _{1– x} Si _x S ₅ I for All-Solid-State Batteries Lee, Yongheum; Jeong, Jiwon; Lim, Hee-Dae ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 1 https://doi.org/10.1021/acssuschemeng.0c05549	journal	December 2020
SoftBV – a software tool for screening the materials genome of inorganic fast ion conductors Chen, Haomin; Wong, Lee Loong; Adams, Stefan Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 75, Issue 1 https://doi.org/10.1107/S2052520618015718	journal	January 2019
Lithium Ytterbium-Based Halide Solid Electrolytes for High Voltage All-Solid-State Batteries Kim, Se Young; Kaup, Kavish; Park, Kern-Ho ACS Materials Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsmaterialslett.1c00142	journal	June 2021
High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory Xiao, Ruijuan; Li, Hong; Chen, Liquan Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14227	journal	September 2015
�ber Alkali-hexachlorochromate(III): Na3CrCl6 Friedrich, G.; Fink, H.; Seifert, H. J. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 548, Issue 5 https://doi.org/10.1002/zaac.19875480516	journal	May 1987
Progress in the Development of Sodium-Ion Solid Electrolytes Kim, Jung-Joon; Yoon, Kyungho; Park, Inchul Small Methods, Vol. 1, Issue 10 https://doi.org/10.1002/smtd.201700219	journal	September 2017
Advanced High‐Voltage All‐Solid‐State Li‐Ion Batteries Enabled by a Dual‐Halogen Solid Electrolyte Zhang, Shumin; Zhao, Feipeng; Wang, Shuo Advanced Energy Materials, Vol. 11, Issue 32 https://doi.org/10.1002/aenm.202100836	journal	July 2021
Electrolyte and Interface Engineering for Solid-State Sodium Batteries Lu, Yong; Li, Lin; Zhang, Qiu Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.07.028	journal	September 2018
Machine Learning-Assisted Discovery of Solid Li-Ion Conducting Materials Sendek, Austin D.; Cubuk, Ekin D.; Antoniuk, Evan R. Chemistry of Materials, Vol. 31, Issue 2 https://doi.org/10.1021/acs.chemmater.8b03272	journal	November 2018
Yttrium–Sodium Halides as Promising Solid-State Electrolytes with High Ionic Conductivity and Stability for Na-Ion Batteries Qie, Yu; Wang, Shuo; Fu, Sijie The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00010	journal	April 2020
Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries Park, Dongsu; Park, Haesun; Lee, Yongheum ACS Applied Materials & Interfaces, Vol. 12, Issue 31 https://doi.org/10.1021/acsami.0c07003	journal	July 2020
Thermodynamic Assessment of Coating Materials for Solid-State Li, Na, and K Batteries Yu, Seungho; Park, Haesun; Siegel, Donald J. ACS Applied Materials & Interfaces, Vol. 11, Issue 40 https://doi.org/10.1021/acsami.9b11001	journal	September 2019
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Solid Halide Electrolytes with High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries Asano, Tetsuya; Sakai, Akihiro; Ouchi, Satoru Advanced Materials, Vol. 30, Issue 44 https://doi.org/10.1002/adma.201803075	journal	September 2018
Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors Liu, Yunsheng; Wang, Shuo; Nolan, Adelaide M. Advanced Energy Materials, Vol. 10, Issue 40 https://doi.org/10.1002/aenm.202002356	journal	September 2020
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Development of solid-state electrolytes for sodium-ion battery–A short review Wang, Yumei; Song, Shufeng; Xu, Chaohe Nano Materials Science, Vol. 1, Issue 2 https://doi.org/10.1016/j.nanoms.2019.02.007	journal	June 2019
Solid electrolytes and interfaces in all-solid-state sodium batteries: Progress and perspective Hou, Wenru; Guo, Xianwei; Shen, Xuyang Nano Energy, Vol. 52 https://doi.org/10.1016/j.nanoen.2018.07.036	journal	October 2018
Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li _{3– x} In _{1– x} Zr _x Cl ₆ (0 ≤ x ≤ 0.5) Helm, Bianca; Schlem, Roman; Wankmiller, Björn Chemistry of Materials, Vol. 33, Issue 12 https://doi.org/10.1021/acs.chemmater.1c01348	journal	June 2021
A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries Wu, Erik A.; Banerjee, Swastika; Tang, Hanmei Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21488-7	journal	February 2021
Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
Metal Halide Superionic Conductors for All-Solid-State Batteries Liang, Jianwen; Li, Xiaona; Adair, Keegan R. Accounts of Chemical Research, Vol. 54, Issue 4 https://doi.org/10.1021/acs.accounts.0c00762	journal	January 2021
Site-Occupation-Tuned Superionic Li _x ScCl _{3+ x} Halide Solid Electrolytes for All-Solid-State Batteries Liang, Jianwen; Li, Xiaona; Wang, Shuo Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00134	journal	March 2020
Na ₁₁ Sn ₂ PS ₁₂ : a new solid state sodium superionic conductor Zhang, Z.; Ramos, E.; Lalère, F. Energy & Environmental Science, Vol. 11, Issue 1 https://doi.org/10.1039/C7EE03083E	journal	January 2018
Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability Wang, Shuo; Bai, Qiang; Nolan, Adelaide M. Angewandte Chemie International Edition, Vol. 58, Issue 24 https://doi.org/10.1002/anie.201901938	journal	June 2019
The chlorides Na3MCl6 (M ? Eu?Lu, Y, Sc): Synthesis, crystal structures, and thermal behaviour Meyer, Gerd; Peter Ax, Studienrat; Schleid, Thomas Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 554, Issue 11 https://doi.org/10.1002/zaac.19875541104	journal	November 1987
New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe ³⁺ ‐Substituted Li ₂ ZrCl ₆ Kwak, Hiram; Han, Daseul; Lyoo, Jeyne Advanced Energy Materials, Vol. 11, Issue 12 https://doi.org/10.1002/aenm.202003190	journal	January 2021
Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries Riegger, Luise M.; Schlem, Roman; Sann, Joachim Angewandte Chemie International Edition, Vol. 60, Issue 12 https://doi.org/10.1002/anie.202015238	journal	February 2021
Na _{3– x} Er _{1– x} Zr _x Cl ₆ —A Halide-Based Fast Sodium-Ion Conductor with Vacancy-Driven Ionic Transport Schlem, Roman; Banik, Ananya; Eckardt, Mirco ACS Applied Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsaem.0c01870	journal	September 2020
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries Albertus, Paul; Babinec, Susan; Litzelman, Scott Nature Energy, Vol. 3, Issue 1 https://doi.org/10.1038/s41560-017-0047-2	journal	December 2017
Defect-Mediated Conductivity Enhancements in Na _{3– x} Pn _{1– x} W _x S ₄ (Pn = P, Sb) Using Aliovalent Substitutions Fuchs, Till; Culver, Sean P.; Till, Paul ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02537	journal	November 2019
Understanding interface stability in solid-state batteries Xiao, Yihan; Wang, Yan; Bo, Shou-Hang Nature Reviews Materials, Vol. 5, Issue 2 https://doi.org/10.1038/s41578-019-0157-5	journal	December 2019
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Na2ZrCl6 enabling highly stable 3 V all-solid-state Na-ion batteries Kwak, Hiram; Lyoo, Jeyne; Park, Juhyoun Energy Storage Materials, Vol. 37 https://doi.org/10.1016/j.ensm.2021.01.026	journal	May 2021
Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations Tang, Hanmei; Deng, Zhi; Lin, Zhuonan Chemistry of Materials, Vol. 30, Issue 1 https://doi.org/10.1021/acs.chemmater.7b04096	journal	December 2017

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