Fluorine-Substituted Lithium Chloride Solid Electrolytes for High-Voltage All-Solid-State Lithium-Ion Batteries

Kim, Sooyeon; Lee, Yongheum; Kim, Kwangnam; Wood, Brandon C.; Han, Sang Soo; Yu, Seungho

doi:10.1021/acsenergylett.3c02307

Fluorine-Substituted Lithium Chloride Solid Electrolytes for High-Voltage All-Solid-State Lithium-Ion Batteries

Journal Article · Mon Dec 04 04:00:00 EST 2023 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.3c02307· OSTI ID:2309844

^[1]; Lee, Yongheum ^[2]; ^[3]; ^[3]; ^[1]; ^[4]

Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of). Computational Science Research Center
Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of). Energy Storage Research Center
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of). Energy Storage Research Center; Korea University of Science and Technology, Seoul (Korea, Republic of)

Lithium ternary halides are promising solid electrolytes, owing to their high ionic conductivity and reasonably high oxidative and chemical stability. Recently, fluorine substitution in Li₃MCl₆ has been suggested as a promising approach for further enhancing oxidation stability. Accordingly, this study outlines a material design strategy for F-substituted Li₃MCl₆ through systematic theoretical analyses. Calculations reveal that the mixing limit of F in Li₃MCl_6–xF_x is in the range of 0.5–1.5, and the resulting Li₃MCl_6–xF_x phases can retain ionic conductivity above 1 mS/cm up to x = 1.0. Additionally, the calculations also predict that the formation of F-containing passivating phases could increase the oxidation potential for Li3MCl5F to ~6.3 V. The proposed material design strategy is validated through the synthesis of Li₃YCl₅F, which is confirmed to show both high ionic conductivity and enhanced oxidation stability. The design guidelines presented herein can accelerate the potential use of halide-based electrolyte chemistries in high-voltage all-solid-state batteries.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2309844

Report Number(s):: LLNL--JRNL-854279; 1082487

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 1 Vol. 9; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

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
Fluorinated Li₁₀GeP₂S₁₂ Enables Stable All‐Solid‐State Lithium Batteries Jin, Yuming; He, Qinsheng; Liu, Gaozhan Advanced Materials, Vol. 35, Issue 19 https://doi.org/10.1002/adma.202211047	journal	March 2023
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
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
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
A Series of Ternary Metal Chloride Superionic Conductors for High‐Performance All‐Solid‐State Lithium Batteries Liang, Jianwen; van der Maas, Eveline; Luo, Jing Advanced Energy Materials, Vol. 12, Issue 21 https://doi.org/10.1002/aenm.202103921	journal	April 2022
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
Formation of LiF‐rich Cathode‐Electrolyte Interphase by Electrolyte Reduction Bai, Panxing; Ji, Xiao; Zhang, Jiaxun Angewandte Chemie International Edition, Vol. 61, Issue 26 https://doi.org/10.1002/anie.202202731	journal	April 2022
Interphase Stabilization of LiNi_0.5Mn_1.5O₄ Cathode for 5 V‐Class All‐Solid‐State Batteries Lee, Dongsoo; Cui, Zehao; Goodenough, John B. Small, Vol. 20, Issue 2 https://doi.org/10.1002/smll.202306053	journal	September 2023
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
Improved stability against moisture and lithium metal by doping F into Li3InCl6 Chen, Xin; Jia, Zhiqing; Lv, Hanmei Journal of Power Sources, Vol. 545 https://doi.org/10.1016/j.jpowsour.2022.231939	journal	October 2022
Recent development of lithium argyrodite solid-state electrolytes for solid-state batteries: Synthesis, structure, stability and dynamics Yu, Chuang; Zhao, Feipeng; Luo, Jing Nano Energy, Vol. 83 https://doi.org/10.1016/j.nanoen.2021.105858	journal	May 2021
Revealing the Pnma crystal structure and ion-transport mechanism of the Li3YCl6 solid electrolyte Hu, Lv; Zhu, Jinze; Duan, Chaomin Cell Reports Physical Science, Vol. 4, Issue 6 https://doi.org/10.1016/j.xcrp.2023.101428	journal	June 2023
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
Long-Term Cyclability of NCM-811 at High Voltages in Lithium-Ion Batteries: an In-Depth Diagnostic Study Li, Wangda; Liu, Xiaoming; Xie, Qiang Chemistry of Materials, Vol. 32, Issue 18 https://doi.org/10.1021/acs.chemmater.0c02398	journal	August 2020
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
Unlocking the Potential of Fluoride-Based Solid Electrolytes for Solid-State Lithium Batteries Feinauer, Max; Euchner, Holger; Fichtner, Maximilian ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b01166	journal	September 2019
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
Computational Investigation of the Interfacial Stability of Lithium Chloride Solid Electrolytes in All-Solid-State Lithium Batteries Chun, Gin Hyung; Shim, Joon Hyung; Yu, Seungho ACS Applied Materials & Interfaces, Vol. 14, Issue 1 https://doi.org/10.1021/acsami.1c22104	journal	December 2021
Mitigating the Interfacial Degradation in Cathodes for High-Performance Oxide-Based Solid-State Lithium Batteries Wang, Dawei; Sun, Qian; Luo, Jing ACS Applied Materials & Interfaces, Vol. 11, Issue 5 https://doi.org/10.1021/acsami.8b17881	journal	January 2019
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
Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications Kwak, Hiram; Wang, Shuo; Park, Juhyoun ACS Energy Letters, Vol. 7, Issue 5 https://doi.org/10.1021/acsenergylett.2c00438	journal	April 2022
Enabling a Co-Free, High-Voltage LiNi_0.5Mn_1.5O₄ Cathode in All-Solid-State Batteries with a Halide Electrolyte Jang, Jihyun; Chen, Yu-Ting; Deysher, Grayson ACS Energy Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acsenergylett.2c01397	journal	July 2022
Electrochemical Window of the Li-Ion Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Thompson, Travis; Yu, Seungho; Williams, Logan ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00593	journal	January 2017
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
High-Throughput Computational Screening of Li-Containing Fluorides for Battery Cathode Coatings Liu, Bo; Wang, Da; Avdeev, Maxim ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 2 https://doi.org/10.1021/acssuschemeng.9b05557	journal	December 2019
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
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
Stacking Faults Assist Lithium-Ion Conduction in a Halide-Based Superionic Conductor Sebti, Elias; Evans, Hayden A.; Chen, Hengning Journal of the American Chemical Society, Vol. 144, Issue 13 https://doi.org/10.1021/jacs.1c11335	journal	March 2022
New Family of Argyrodite Thioantimonate Lithium Superionic Conductors Zhou, Laidong; Assoud, Abdeljalil; Zhang, Qiang Journal of the American Chemical Society, Vol. 141, Issue 48 https://doi.org/10.1021/jacs.9b08357	journal	October 2019
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
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
A lithium superionic conductor Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro Nature Materials, Vol. 10, Issue 9, p. 682-686 https://doi.org/10.1038/nmat3066	journal	July 2011
A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries Wang, Kai; Ren, Qingyong; Gu, Zhenqi Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24697-2	journal	July 2021
Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries Kwak, Hiram; Kim, Jae-Seung; Han, Daseul Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-38037-z	journal	April 2023
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
Benchmarking the performance of all-solid-state lithium batteries Randau, Simon; Weber, Dominik A.; Kötz, Olaf Nature Energy, Vol. 5, Issue 3 https://doi.org/10.1038/s41560-020-0565-1	journal	March 2020
High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes Zhou, Laidong; Zuo, Tong-Tong; Kwok, Chun Yuen Nature Energy, Vol. 7, Issue 1 https://doi.org/10.1038/s41560-021-00952-0	journal	January 2022
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
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
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
Developing high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects Liang, Gemeng; Peterson, Vanessa K.; See, Khay Wai Journal of Materials Chemistry A, Vol. 8, Issue 31 https://doi.org/10.1039/D0TA02812F	journal	January 2020
All-solid-state lithium batteries enabled by sulfide electrolytes: from fundamental research to practical engineering design Wang, Changhong; Liang, Jianwen; Zhao, Yang Energy & Environmental Science, Vol. 14, Issue 5 https://doi.org/10.1039/D1EE00551K	journal	January 2021
Structural design strategies for superionic sodium halide solid electrolytes Yu, Seungho; Kim, Kwangnam; Wood, Brandon C. Journal of Materials Chemistry A, Vol. 10, Issue 45 https://doi.org/10.1039/D2TA05158C	journal	January 2022
Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina APL Materials, Vol. 6, Issue 4 https://doi.org/10.1063/1.5011378	journal	April 2018
The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium He, Mingfu; Guo, Rui; Hobold, Gustavo M. Proceedings of the National Academy of Sciences, Vol. 117, Issue 1 https://doi.org/10.1073/pnas.1911017116	journal	December 2019
Prospects of halide-based all-solid-state batteries: From material design to practical application Wang, Changhong; Liang, Jianwen; Kim, Jung Tae Science Advances, Vol. 8, Issue 36 https://doi.org/10.1126/sciadv.adc9516	journal	September 2022
Effect of Fluorine Substitution in Li₃YCl₆ Chloride Solid Electrolytes for All-solid-state Battery Yamagishi, Mariya; Zhong, Chengchao; Shibata, Daisuke Electrochemistry, Vol. 91, Issue 3 https://doi.org/10.5796/electrochemistry.23-00005	journal	March 2023

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