High‐Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential

Wu, Min; Wang, Zeyi; Zhang, Weiran; Jayawardana, Chamithri; Li, Yue; Chen, Fu; Nan, Bo; Lucht, Brett L.; Wang, Chunsheng

doi:10.1002/ange.202216169

Title: High‐Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential

Journal Article · 17 January 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202216169 · OSTI ID:1909950

^[1]; Wang, Zeyi ^[1]; Zhang, Weiran ^[2]; Jayawardana, Chamithri ^[3]; Li, Yue ^[4]; Chen, Fu ^[4]; Nan, Bo ^[4]; Lucht, Brett L. ^[3];

^[5]

Department of Chemical and Biomolecular Engineering University of Maryland College Park MD 20742 USA
Department of Materials Science &, Engineering University of Maryland College Park MD 20742 USA
Department of Chemistry University of Rhode Island Kingston RI 02881 USA
Department of Chemistry and Biochemistry University of Maryland College Park MD 20742 USA
Department of Chemical and Biomolecular Engineering University of Maryland College Park MD 20742 USA, Department of Materials Science &, Engineering University of Maryland College Park MD 20742 USA

Abstract Electrolyte engineering is crucial for developing high‐performance lithium metal batteries (LMB). Here, we synthesized two cosolvents methyl bis(fluorosulfonyl)imide (MFSI) and 3,3,4,4‐tetrafluorotetrahydrofuran (TFF) with significantly different reduction potentials and add them into LiFSI‐DME electrolytes. The LiFSI/TFF‐DME electrolyte gave an average Li Coulombic efficiency (CE) of 99.41 % over 200 cycles, while the average Li CEs for MFSI‐based electrolyte is only 98.62 %. Additionally, the TFF‐based electrolytes exhibited a more reversible performance than the state‐of‐the‐art fluorinated 1,4‐dimethoxylbutane electrolyte in both Li||Cu half‐cell and anode‐free Cu||LiNi _0.8 Mn _0.1 Co _0.1 O ₂ full cell. More importantly, the decomposition product from bis(fluorosulfonyl)imide anion could react with ether solvent, which destroyed the SEI, thus decreasing cell performance. These key discoveries provide new insights into the rational design of electrolyte solvents and cosolvents for LMB.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1909950

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 8 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (30)

Dual‐Solvent Li‐Ion Solvation Enables High‐Performance Li‐Metal Batteries Wang, Hansen; Yu, Zhiao; Kong, Xian Advanced Materials, Vol. 33, Issue 25 https://doi.org/10.1002/adma.202008619	journal	May 2021
Designing and Demystifying the Lithium Metal Interface toward Highly Reversible Batteries (Adv. Mater. 52/2021) Xu, Rui; Ding, Jun‐Fan; Ma, Xia‐Xia Advanced Materials, Vol. 33, Issue 52 https://doi.org/10.1002/adma.202170413	journal	December 2021
Regulating Interfacial Chemistry in Lithium‐Ion Batteries by a Weakly Solvating Electrolyte** Yao, Yu‐Xing; Chen, Xiang; Yan, Chong Angewandte Chemie, Vol. 133, Issue 8 https://doi.org/10.1002/ange.202011482	journal	November 2020
Regulating Interfacial Chemistry in Lithium‐Ion Batteries by a Weakly Solvating Electrolyte** Yao, Yu‐Xing; Chen, Xiang; Yan, Chong Angewandte Chemie International Edition, Vol. 60, Issue 8 https://doi.org/10.1002/anie.202011482	journal	November 2020
Practical High‐Voltage Lithium Metal Batteries Enabled by Tuning the Solvation Structure in Weakly Solvating Electrolyte Pham, Thuy Duong; Bin Faheem, Abdullah; Kim, Junam Small, Vol. 18, Issue 14 https://doi.org/10.1002/smll.202107492	journal	February 2022
Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries Fan, Xiulin; Chen, Long; Ji, Xiao Chem, Vol. 4, Issue 1 https://doi.org/10.1016/j.chempr.2017.10.017	journal	January 2018
High-Efficiency Lithium Metal Batteries with Fire-Retardant Electrolytes Chen, Shuru; Zheng, Jianming; Yu, Lu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.05.002	journal	August 2018
Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions Ren, Xiaodi; Zou, Lianfeng; Cao, Xia Joule, Vol. 3, Issue 7 https://doi.org/10.1016/j.joule.2019.05.006	journal	July 2019
Natural abundance 17O, 6Li NMR and molecular modeling studies of the solvation structures of lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane liquid electrolytes Wan, Chuan; Hu, Mary Y.; Borodin, Oleg Journal of Power Sources, Vol. 307 https://doi.org/10.1016/j.jpowsour.2015.12.120	journal	March 2016
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
Designing Weakly Solvating Solid Main-Chain Fluoropolymer Electrolytes: Synergistically Enhancing Stability toward Li Anodes and High-Voltage Cathodes Ma, Mingyu; Shao, Fei; Wen, Peng ACS Energy Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acsenergylett.1c02036	journal	November 2021
Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery Chen, Yuelang; Yu, Zhiao; Rudnicki, Paul Journal of the American Chemical Society, Vol. 143, Issue 44 https://doi.org/10.1021/jacs.1c09006	journal	October 2021
Why Bis(fluorosulfonyl)imide Is a “Magic Anion” for Electrochemistry Shkrob, Ilya A.; Marin, Timothy W.; Zhu, Ye The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp506567p	journal	August 2014
High rate and stable cycling of lithium metal anode Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7362	journal	February 2015
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
Fluorinated ether electrolyte with controlled solvation structure for high voltage lithium metal batteries Zhao, Yan; Zhou, Tianhong; Ashirov, Timur Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-29199-3	journal	May 2022
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
Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries Zeng, Ziqi; Murugesan, Vijayakumar; Han, Kee Sung Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0196-y	journal	July 2018
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization Cao, Xia; Ren, Xiaodi; Zou, Lianfeng Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0464-5	journal	September 2019
Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries Yu, Zhiao; Wang, Hansen; Kong, Xian Nature Energy, Vol. 5, Issue 7 https://doi.org/10.1038/s41560-020-0634-5	journal	June 2020
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes Hobold, Gustavo M.; Lopez, Jeffrey; Guo, Rui Nature Energy, Vol. 6, Issue 10 https://doi.org/10.1038/s41560-021-00910-w	journal	October 2021
Rational solvent molecule tuning for high-performance lithium metal battery electrolytes Yu, Zhiao; Rudnicki, Paul E.; Zhang, Zewen Nature Energy, Vol. 7, Issue 1 https://doi.org/10.1038/s41560-021-00962-y	journal	January 2022
Fire-extinguishing, recyclable liquefied gas electrolytes for temperature-resilient lithium-metal batteries Yin, Yijie; Yang, Yangyuchen; Cheng, Diyi Nature Energy, Vol. 7, Issue 6 https://doi.org/10.1038/s41560-022-01051-4	journal	June 2022
Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries Fan, Xiulin; Chen, Long; Borodin, Oleg Nature Nanotechnology, Vol. 13, Issue 8 https://doi.org/10.1038/s41565-018-0183-2	journal	July 2018
FSI-inspired solvent and “full fluorosulfonyl” electrolyte for 4 V class lithium-metal batteries Xue, Weijiang; Shi, Zhe; Huang, Mingjun Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02538C	journal	January 2020
Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries Suo, Liumin; Xue, Weijiang; Gobet, Mallory Proceedings of the National Academy of Sciences, Vol. 115, Issue 6 https://doi.org/10.1073/pnas.1712895115	journal	January 2018
High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes Shi, Qiuwei; Zhong, Yiren; Wu, Min Proceedings of the National Academy of Sciences, Vol. 115, Issue 22 https://doi.org/10.1073/pnas.1803634115	journal	May 2018
Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries Cao, Xia; Gao, Peiyuan; Ren, Xiaodi Proceedings of the National Academy of Sciences, Vol. 118, Issue 9 https://doi.org/10.1073/pnas.2020357118	journal	February 2021
Self-assembled monolayers direct a LiF-rich interphase toward long-life lithium metal batteries Liu, Yujing; Tao, Xinyong; Wang, Yao Science, Vol. 375, Issue 6582 https://doi.org/10.1126/science.abn1818	journal	February 2022

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