Advanced All-Fluorinated Electrolytes for Extended Cycle Life and Stability of Li||SPAN Batteries

Kim, Ju-Myung; Ospina-Acevedo, Francisco A.; Cao, Xia; Miao, Qiushi; Wang, Nan; Yu, Sicen; Li, Zheng; Engelhard, Mark H.; Hu, Enyuan; Seminario, Jorge M.; Wang, Chunsheng; Liu, Ping; Balbuena, Perla B.; Liu, Jun; Zhang, Ji-Guang; Xu, Wu

doi:10.1021/acsenergylett.5c03054

Title: Advanced All-Fluorinated Electrolytes for Extended Cycle Life and Stability of Li||SPAN Batteries

Journal Article · Fri Dec 26 00:00:00 UTC 2025 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.5c03054 · OSTI ID:3013662

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Texas A & M Univ., College Station, TX (United States)
Univ. of California, San Diego, CA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Univ. of Washington, Seattle, WA (United States)
Univ. of Maryland, College Park, MD (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)

Achieving long-term stability and consistent capacity in lithium (Li) metal batteries with sulfurized polyacrylonitrile (SPAN) cathodes requires precisely engineered electrolytes to optimize interphase formation and redox reversibility. Here, this study presents 1,1-difluoro-2-(2-methoxyethoxy)ethane (DFE)-based localized high-concentration electrolytes (LHCEs), incorporating fluorinated components such as salt, solvating solvent, and diluent for improved electrode stability. Molecular dynamics simulations and surface analyses reveal that the DFE-LHCE with 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (BTFEE) diluent produces uniform and robust interphase layers on both cathode and anode, enriched with inorganic species like LiF and Li₂O. These properties lead to prolonged redox reversibility of the SPAN cathode, suppressed side reactions, and extended cycle life for Li||SPAN cells. Remarkably, DFE-BTFEE-LHCE enables Li||SPAN coin cells with an areal capacity of ∼7 mAh cm^-2 for SPAN to retain 81.3% capacity after 200 cycles and pouch cells of 0.12 Ah with 8 mAh cm^-2 of SPAN and lean electrolyte to maintain 96.4% capacity over 80 cycles. These findings pave the way for advancing Li||SPAN battery technologies.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0012704

OSTI ID:: 3013662

Report Number(s):: BNL--229337-2026-JAAM

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 1 Vol. 11; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

A Novel Conductive Polymer-Sulfur Composite Cathode Material for Rechargeable Lithium Batteries Wang, J.; Yang, J.; Xie, J. Advanced Materials, Vol. 14, Issue 13-14, p. 963-965 https://doi.org/10.1002/1521-4095(20020705)14:13/14<963::AID-ADMA963>3.0.CO;2-P	journal	July 2002
Critical Review of Fluorinated Electrolytes for High‐Performance Lithium Metal Batteries Li, Zhongzhe; Chen, Yufang; Yun, Xiaoru Advanced Functional Materials, Vol. 33, Issue 32 https://doi.org/10.1002/adfm.202300502	journal	April 2023
Enhancing Cycling Stability of Lithium Metal Batteries by a Bifunctional Fluorinated Ether Tran, Thanh‐Nhan; Cao, Xia; Xu, Yaobin Advanced Functional Materials, Vol. 34, Issue 42 https://doi.org/10.1002/adfm.202407012	journal	July 2024
Advances in Lithium–Sulfur Batteries: From Academic Research to Commercial Viability Chen, Yi; Wang, Tianyi; Tian, Huajun Advanced Materials, Vol. 33, Issue 29 https://doi.org/10.1002/adma.202003666	journal	June 2021
Lithium‐Metal Batteries: From Fundamental Research to Industrialization Kim, Sujin; Park, Gyuleen; Lee, Seung Jong Advanced Materials, Vol. 35, Issue 43 https://doi.org/10.1002/adma.202206625	journal	March 2023
Electrolyte Regulation towards Stable Lithium‐Metal Anodes in Lithium–Sulfur Batteries with Sulfurized Polyacrylonitrile Cathodes Chen, Wei‐Jing; Li, Bo‐Quan; Zhao, Chang‐Xin Angewandte Chemie International Edition, Vol. 59, Issue 27 https://doi.org/10.1002/anie.201912701	journal	April 2020
XPS analysis of a lithium surface immersed in propylene carbonate solution containing various salts Kanamura, Kiyoshi; Tamura, Hiroshi; Takehara, Zen-ichiro Journal of Electroanalytical Chemistry, Vol. 333, Issue 1-2 https://doi.org/10.1016/0022-0728(92)80386-I	journal	July 1992
Recent advances in shuttle effect inhibition for lithium sulfur batteries Ren, Wenchen; Ma, Wei; Zhang, Shufen Energy Storage Materials, Vol. 23 https://doi.org/10.1016/j.ensm.2019.02.022	journal	December 2019
Cathode electrolyte interface enabling stable Li–S batteries Xing, Xing; Li, Yejing; Wang, Xuefeng Energy Storage Materials, Vol. 21 https://doi.org/10.1016/j.ensm.2019.06.022	journal	September 2019
Solid electrolyte interphases in lithium metal batteries Jagger, Ben; Pasta, Mauro Joule, Vol. 7, Issue 10 https://doi.org/10.1016/j.joule.2023.08.007	journal	October 2023
Suppression of polysulfide dissolution by polypyrrole modification of sulfur-based cathodes in lithium secondary batteries Nakamura, Natsuki; Yokoshima, Tokihiko; Nara, Hiroki Journal of Power Sources, Vol. 274 https://doi.org/10.1016/j.jpowsour.2014.10.192	journal	January 2015
Constructing lithium oxysulfide-rich solid electrolyte interphase to shield polysulfides in practical lithium–sulfur batteries Hou, Li-Peng; Li, Xi-Yao; Bi, Chen-Xi Journal of Power Sources, Vol. 550 https://doi.org/10.1016/j.jpowsour.2022.232144	journal	December 2022
An all-fluorinated electrolyte with 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether as co-solvent for lithium-ion cells with advanced electrochemical and safety properties at high voltage Ouyang, Dongxu; Liu, Bo; Wan, Xiaotian Journal of Power Sources, Vol. 615 https://doi.org/10.1016/j.jpowsour.2024.235095	journal	September 2024
Enhanced lithium battery cathode performance via mechanical grinding of CFx_MnO2 hybrid materials for space-grade applications: Unveiling synergistic effects Dauga, Louise; Haddad, Guillaume; Foix, Dominique Synthetic Metals, Vol. 307 https://doi.org/10.1016/j.synthmet.2024.117660	journal	September 2024
Pinned Electrode/Electrolyte Interphase and Its Formation Origin for Sulfurized Polyacrylonitrile Cathode in Stable Lithium Batteries Zhang, Xianhui; Gao, Peiyuan; Wu, Zhaohui ACS Applied Materials & Interfaces, Vol. 14, Issue 46 https://doi.org/10.1021/acsami.2c16890	journal	November 2022
Tailoring Solvation Solvent in Localized High-Concentration Electrolytes for Lithium\|\|Sulfurized Polyacrylonitrile Kim, Ju-Myung; Gao, Peiyuan; Miao, Qiushi ACS Applied Materials & Interfaces https://doi.org/10.1021/acsami.4c02326	journal	April 2024
Role of Inorganic Surface Layer on Solid Electrolyte Interphase Evolution at Li-Metal Anodes Kamphaus, Ethan P.; Angarita-Gomez, Stefany; Qin, Xueping ACS Applied Materials & Interfaces, Vol. 11, Issue 34 https://doi.org/10.1021/acsami.9b07587	journal	August 2019
A Perspective toward Practical Lithium–Sulfur Batteries Zhao, Meng; Li, Bo-Quan; Zhang, Xue-Qiang ACS Central Science, Vol. 6, Issue 7 https://doi.org/10.1021/acscentsci.0c00449	journal	June 2020
Dual Passivation of Cathode and Anode through Electrode–Electrolyte Interface Engineering Enables Long-Lifespan Li Metal–SPAN Batteries He, Yubin; Zou, Peichao; Bak, Seong-Min ACS Energy Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsenergylett.2c01093	journal	August 2022
Structural and Interphasial Stabilities of Sulfurized Polyacrylonitrile (SPAN) Cathode Tan, Sha; Rahman, Muhammad Mominur; Wu, Zhaohui ACS Energy Letters, Vol. 8, Issue 6 https://doi.org/10.1021/acsenergylett.3c00281	journal	May 2023
Electrolyte Engineering for Long-Life Li-SPAN Batteries Miao, Qiushi; Solan, Nicholas; Hyun, Gayea ACS Energy Letters, Vol. 8, Issue 11 https://doi.org/10.1021/acsenergylett.3c01711	journal	October 2023
Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface Kuai, Dacheng; Wang, Shen; Perez-Beltran, Saul ACS Energy Letters, Vol. 9, Issue 3 https://doi.org/10.1021/acsenergylett.3c02757	journal	February 2024
Synchronized Breathing in Anion-Derived Interphases Tan, Sha; Xia, Kangxuan; Wang, Nan ACS Energy Letters, Vol. 10, Issue 8 https://doi.org/10.1021/acsenergylett.5c01756	journal	July 2025
New Insights on the Good Compatibility of Ether-Based Localized High-Concentration Electrolyte with Lithium Metal Li, Tao; Li, Yan; Sun, Yiling ACS Materials Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsmaterialslett.1c00276	journal	May 2021
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
Structural Transformation in a Sulfurized Polymer Cathode to Enable Long-Life Rechargeable Lithium–Sulfur Batteries Wang, Shen; Lu, Bingyu; Cheng, Diyi Journal of the American Chemical Society, Vol. 145, Issue 17 https://doi.org/10.1021/jacs.3c00628	journal	April 2023
Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries Li, Zheng; Rao, Harsha; Atwi, Rasha Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-36647-1	journal	February 2023
Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries Wu, Feixiang; Maier, Joachim; Yu, Yan Chemical Society Reviews, Vol. 49, Issue 5 https://doi.org/10.1039/C7CS00863E	journal	January 2020
Sulfurized polyacrylonitrile for high-performance lithium sulfur batteries: advances and prospects Zhao, Xiaohui; Wang, Chonglong; Li, Ziwei Journal of Materials Chemistry A, Vol. 9, Issue 35 https://doi.org/10.1039/D1TA03300J	journal	January 2021
Solvent selection criteria for temperature-resilient lithium–sulfur batteries Cai, Guorui; Holoubek, John; Li, Mingqian Proceedings of the National Academy of Sciences, Vol. 119, Issue 28 https://doi.org/10.1073/pnas.2200392119	journal	July 2022

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