Enhancing Cycling Stability of Lithium Metal Batteries by a Bifunctional Fluorinated Ether

Tran, Thanh‐Nhan; Cao, Xia; Xu, Yaobin; Gao, Peiyuan; Zhou, Hui; Guo, Fenghua; Han, Kee Sung; Liu, Dianying; Le, Phung ML; Weller, J. Mark; Engelhard, Mark H.; Wang, Chongmin; Whittingham, M. Stanley; Xu, Wu; Zhang, Ji‐Guang

doi:10.1002/adfm.202407012

Enhancing Cycling Stability of Lithium Metal Batteries by a Bifunctional Fluorinated Ether

Journal Article · Wed Jul 03 00:00:00 EDT 2024 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202407012· OSTI ID:2391051

^[1]; ^[1]; ^[2]; ^[3]; ^[4]; Guo, Fenghua ^[4]; ^[3]; Liu, Dianying ^[1]; ^[1]; ^[1]; ^[1]; ^[2]; ^[4]; ^[1]; ^[1]

Energy and Environmental Directorate Pacific Northwest National Laboratory Richland WA 99354 USA
Environmental and Molecular Sciences Laboratory Pacific Northwest National Laboratory Richland WA 99354 USA
Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland WA 99354 USA
Department of Chemistry State University of New York at Binghamton Binghamton NY 13902 USA

Abstract

The lifespan of lithium (Li) metal batteries (LMBs) can be greatly improved by the formation of inorganic‐rich electrode‐electrolyte interphases (EEIs) (including solid‐electrolyte interphase on anode and cathode‐electrolyte interphase on cathode). In this work, a localized high‐concentration electrolyte containing lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2‐dimethoxyethane (DME) solvent and 1,2‐bis(1,1,2,2‐tetrafluoroethoxy)ethane (BTFEE) diluent is optimized. BTFEE is a fluorinated ether with weakly‐solvating ability for LiFSI so it also acts as a co‐solvent in this electrolyte. It can facilitate anion decomposition at electrode surfaces and promote the formation of more inorganic‐rich EEI layers. With an optimized molar ratio of LiFSI:DME:BTFEE = 1:1.15:3, LMBs with a high loading (4 mAh cm ⁻² ) lithium nickel manganese cobalt oxide (LiNi _0.8 Mn _0.1 Co _0.1 ) cathode can retain 80% capacity in 470 cycles when cycled in a voltage range of 2.8–4.4 V. The fundamental understanding on the functionality of BTFEE revealed in this work provides new perspectives on the design of practical high‐energy density battery systems.

View Journal Article

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC05-76RL01830

OSTI ID:: 2391051

Alternate ID(s):: OSTI ID: 2530676
OSTI ID: 2473723

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 42 Vol. 34; ISSN 1616-301X

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

Country of Publication:: Germany

Language:: English

References (43)

Electrolyte‐Regulated Solid‐Electrolyte Interphase Enables Long Cycle Life Performance in Organic Cathodes for Potassium‐Ion Batteries Li, Benfang; Zhao, Jin; Zhang, Zihe Advanced Functional Materials https://doi.org/10.1002/adfm.201807137	journal	December 2018
Solvent‐Free Electrolyte for High‐Temperature Rechargeable Lithium Metal Batteries Phan, An L.; Jayawardana, Chamithri; Le, Phung ML Advanced Functional Materials, Vol. 33, Issue 34 https://doi.org/10.1002/adfm.202301177	journal	May 2023
Lithium Fluoride in Electrolyte for Stable and Safe Lithium‐Metal Batteries Tan, Yi‐Hong; Lu, Gong‐Xun; Zheng, Jian‐Hui Advanced Materials, Vol. 33, Issue 42 https://doi.org/10.1002/adma.202102134	journal	September 2021
Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High-Concentration Electrolyte Layer Zheng, Jianming; Yan, Pengfei; Mei, Donghai Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502151	journal	February 2016
Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries Adams, Brian D.; Zheng, Jianming; Ren, Xiaodi Advanced Energy Materials, Vol. 8, Issue 7 https://doi.org/10.1002/aenm.201702097	journal	October 2017
An Anion‐Tuned Solid Electrolyte Interphase with Fast Ion Transfer Kinetics for Stable Lithium Anodes Wang, Zhenxing; Qi, Fulai; Yin, Lichang Advanced Energy Materials, Vol. 10, Issue 14 https://doi.org/10.1002/aenm.201903843	journal	February 2020
Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte Zhai, Pengbo; Liu, Lixuan; Gu, Xiaokang Advanced Energy Materials, Vol. 10, Issue 34 https://doi.org/10.1002/aenm.202001257	journal	July 2020
A High Energy‐Density, Cobalt‐Free, Low‐Nickel LiNi_0.7Mn_0.25Al_0.05O₂ Cathode with a High‐Voltage Electrolyte for Lithium‐Metal Batteries Sim, Richard; Su, Laisuo; Manthiram, Arumugam Advanced Energy Materials, Vol. 13, Issue 21 https://doi.org/10.1002/aenm.202300096	journal	April 2023
Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing Angewandte Chemie International Edition, Vol. 57, Issue 19 https://doi.org/10.1002/anie.201801513	journal	March 2018
An Amphiphilic Molecule‐Regulated Core‐Shell‐Solvation Electrolyte for Li‐Metal Batteries at Ultra‐Low Temperature Shi, Junkai; Xu, Chao; Lai, Jiawei Angewandte Chemie International Edition, Vol. 62, Issue 13 https://doi.org/10.1002/anie.202218151	journal	February 2023
The electrochemical behaviour of tetrahydrofuran and propylene carbonate without added electrolyte Campbell, S. A.; Bowes, C.; McMillan, R. S. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 284, Issue 1 https://doi.org/10.1016/0022-0728(90)87072-R	journal	May 1990
Lithium electrode cycleability and morphology dependence on current density Arakawa, Masayasu; Tobishima, Shin-ichi; Nemoto, Yasue Journal of Power Sources, Vol. 43, Issue 1-3 https://doi.org/10.1016/0378-7753(93)80099-B	journal	March 1993
Analysis of the surface of lithium in organic electrolyte by atomic force microscopy, Fourier transform infrared spectroscopy and scanning auger electron microscopy Morigaki, Ken-ichi; Ohta, Akira Journal of Power Sources, Vol. 76, Issue 2 https://doi.org/10.1016/S0378-7753(98)00151-7	journal	December 1998
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
Localized High-Concentration Sulfone Electrolytes for High-Efficiency Lithium-Metal Batteries Ren, Xiaodi; Chen, Shuru; Lee, Hongkyung Chem, Vol. 4, Issue 8 https://doi.org/10.1016/j.chempr.2018.05.002	journal	August 2018
Electrolyte engineering for highly inorganic solid electrolyte interphase in high-performance lithium metal batteries Zhao, Yan; Zhou, Tianhong; Jeurgens, Lars P. H. Chem, Vol. 9, Issue 3 https://doi.org/10.1016/j.chempr.2022.12.005	journal	March 2023
Cyclic carbonate for highly stable cycling of high voltage lithium metal batteries Su, Chi-Cheung; He, Meinan; Amine, Rachid Energy Storage Materials, Vol. 17 https://doi.org/10.1016/j.ensm.2018.11.003	journal	February 2019
Optimization of fluorinated orthoformate based electrolytes for practical high-voltage lithium metal batteries Cao, Xia; Zou, Lianfeng; Matthews, Bethany E. Energy Storage Materials, Vol. 34 https://doi.org/10.1016/j.ensm.2020.08.035	journal	January 2021
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
A new co-solvent for wide temperature lithium ion battery electrolytes: 2,2,2-Trifluoroethyl n-caproate Lu, Wei; Xie, Kai; Chen, Zhongxue Journal of Power Sources, Vol. 274 https://doi.org/10.1016/j.jpowsour.2014.10.112	journal	January 2015
Anode-originated SEI migration contributes to formation of cathode-electrolyte interphase layer Fang, Shuyu; Jackson, David; Dreibelbis, Mark L. Journal of Power Sources, Vol. 373 https://doi.org/10.1016/j.jpowsour.2017.09.050	journal	January 2018
Electrolytes for high-voltage lithium batteries Jia, Hao; Xu, Wu Trends in Chemistry, Vol. 4, Issue 7 https://doi.org/10.1016/j.trechm.2022.04.010	journal	July 2022
Li ₂ O Solid Electrolyte Interphase: Probing Transport Properties at the Chemical Potential of Lithium Guo, Rui; Gallant, Betar M. Chemistry of Materials, Vol. 32, Issue 13 https://doi.org/10.1021/acs.chemmater.0c00333	journal	May 2020
Lithium Metal Anodes with Nonaqueous Electrolytes Zhang, Ji-Guang; Xu, Wu; Xiao, Jie Chemical Reviews, Vol. 120, Issue 24 https://doi.org/10.1021/acs.chemrev.0c00275	journal	November 2020
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
Lithium Diffusion Mechanism through Solid–Electrolyte Interphase in Rechargeable Lithium Batteries Ramasubramanian, Ajaykrishna; Yurkiv, Vitaliy; Foroozan, Tara The Journal of Physical Chemistry C, Vol. 123, Issue 16 https://doi.org/10.1021/acs.jpcc.9b00436	journal	March 2019
Synergetic Effects of Inorganic Components in Solid Electrolyte Interphase on High Cycle Efficiency of Lithium Ion Batteries Zhang, Qinglin; Pan, Jie; Lu, Peng Nano Letters, Vol. 16, Issue 3 https://doi.org/10.1021/acs.nanolett.5b05283	journal	February 2016
Selecting the Optimal Fluorinated Ether Co-Solvent for Lithium Metal Batteries Su, Chi-Cheung; Amine, Khalil; Cai, Mei ACS Applied Materials & Interfaces, Vol. 15, Issue 2 https://doi.org/10.1021/acsami.2c13034	journal	January 2023
First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF Yildirim, Handan; Kinaci, Alper; Chan, Maria K. Y. ACS Applied Materials & Interfaces, Vol. 7, Issue 34 https://doi.org/10.1021/acsami.5b02904	journal	August 2015
Stable Solid Electrolyte Interphase Formation Induced by Monoquat-Based Anchoring in Lithium Metal Batteries Zhou, Tianhong; Zhao, Yan; El Kazzi, Mario ACS Energy Letters, Vol. 6, Issue 5 https://doi.org/10.1021/acsenergylett.1c00274	journal	April 2021
Voltage and Temperature Limits of Advanced Electrolytes for Lithium-Metal Batteries Buyuker, Isik Su; Pei, Ben; Zhou, Hui ACS Energy Letters, Vol. 8, Issue 4 https://doi.org/10.1021/acsenergylett.3c00235	journal	March 2023
Tailoring Electrolyte Solvation for LiF-Rich Solid Electrolyte Interphase toward a Stable Li Anode Tu, Haifeng; Li, Linge; Wang, Zhicheng ACS Nano, Vol. 16, Issue 10 https://doi.org/10.1021/acsnano.2c06924	journal	September 2022
Beyond LiF: Tailoring Li₂O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries Zeng, Huipeng; Yu, Kai; Li, Jiawei ACS Nano, Vol. 18, Issue 3 https://doi.org/10.1021/acsnano.3c07038	journal	January 2024
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Electrical and Lithium Ion Dynamics in Three Main Components of Solid Electrolyte Interphase from Density Functional Theory Study Chen, Y. C.; Ouyang, C. Y.; Song, L. J. The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp112202s	journal	March 2011
Pathways for practical high-energy long-cycling lithium metal batteries Liu, Jun; Bao, Zhenan; Cui, Yi Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0338-x	journal	February 2019
Understanding and applying coulombic efficiency in lithium metal batteries Xiao, Jie; Li, Qiuyan; Bi, Yujing Nature Energy, Vol. 5, Issue 8 https://doi.org/10.1038/s41560-020-0648-z	journal	June 2020
Quantification of reversible and irreversible lithium in practical lithium-metal batteries Deng, Wei; Yin, Xue; Bao, Wurigumula Nature Energy, Vol. 7, Issue 11 https://doi.org/10.1038/s41560-022-01120-8	journal	September 2022
Direct in situ measurements of electrical properties of solid–electrolyte interphase on lithium metal anodes Xu, Yaobin; Jia, Hao; Gao, Peiyuan Nature Energy, Vol. 8, Issue 12 https://doi.org/10.1038/s41560-023-01361-1	journal	September 2023
Dendrite suppression by anode polishing in zinc-ion batteries Zhang, Zhenyu; Said, Samia; Smith, Keenan Journal of Materials Chemistry A, Vol. 9, Issue 27 https://doi.org/10.1039/D1TA02682H	journal	January 2021
Wide-temperature-range operation of lithium-metal batteries using partially and weakly solvating liquid electrolytes Kim, Saehun; Lee, Jeong-A; Lee, Tae Kyung Energy & Environmental Science, Vol. 16, Issue 11 https://doi.org/10.1039/D3EE02106H	journal	January 2023
Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries Ren, Xiaodi; Gao, Peiyuan; Zou, Lianfeng Proceedings of the National Academy of Sciences, Vol. 117, Issue 46 https://doi.org/10.1073/pnas.2010852117	journal	November 2020
Review—Localized High-Concentration Electrolytes for Lithium Batteries Cao, Xia; Jia, Hao; Xu, Wu Journal of The Electrochemical Society, Vol. 168, Issue 1 https://doi.org/10.1149/1945-7111/abd60e	journal	January 2021

Similar Records

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

Journal Article · Thu Dec 25 19:00:00 EST 2025 · ACS Energy Letters · OSTI ID:3013662

Enhancing Cycling Stability of Lithium Metal Batteries by a Bifunctional Fluorinated Ether

Citation Formats

References (43)

Similar Records

Related Subjects