Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Yu, Zhiao; Wang, Hansen; Kong, Xian; Huang, William; Tsao, Yuchi; Mackanic, David G.; Wang, Kecheng; Wang, Xinchang; Huang, Wenxiao; Choudhury, Snehashis; Zheng, Yu; Amanchukwu, Chibueze V.; Hung, Samantha T.; Ma, Yuting; Lomeli, Eder G.; Qin, Jian; Cui, Yi; Bao, Zhenan

doi:10.1038/s41560-020-0634-5

Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Journal Article · Mon Jun 22 00:00:00 EDT 2020 · Nature Energy

DOI:https://doi.org/10.1038/s41560-020-0634-5· OSTI ID:1647290

^[1]; ^[2]; ^[3]; ^[2]; Tsao, Yuchi ^[4]; ^[3]; Wang, Kecheng ^[2]; Wang, Xinchang ^[5]; Huang, Wenxiao ^[2]; ^[3]; Zheng, Yu ^[1]; Amanchukwu, Chibueze V. ^[3]; ^[6]; Ma, Yuting ^[3]; Lomeli, Eder G. ^[2]; ^[3]; ^[7]; ^[3]

Stanford Univ., CA (United States). Dept. of Chemical Engineering and Dept. of Chemistry
Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
Stanford Univ., CA (United States). Dept. of Chemical Engineering
Stanford Univ., CA (United States). Dept. of Chemical Engineering, Dept. of Chemistry and Dept. of Materials Science and Engineering
Xiamen Univ. (China). School of Electronic Science and Engineering
Stanford Univ., CA (United States). Dept. of Chemistry
Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)

Electrolyte engineering is critical for developing Li metal batteries. While recent works improved Li metal cyclability, a methodology for rational electrolyte design remains lacking. In this study, we propose a design strategy for electrolytes that enable anode-free Li metal batteries with single-solvent single-salt formations at standard concentrations. Rational incorporation of –CF₂– units yields fluorinated 1,4-dimethoxylbutane as the electrolyte solvent. Paired with 1 M lithium bis(fluorosulfonyl)imide, this electrolyte possesses unique Li–F binding and high anion/solvent ratio in the solvation sheath, leading to excellent compatibility with both Li metal anodes (Coulombic efficiency ~ 99.52% and fast activation within five cycles) and high-voltage cathodes (~6 V stability). Fifty-μm-thick Li|NMC batteries retain 90% capacity after 420 cycles with an average Coulombic efficiency of 99.98%. Industrial anode-free pouch cells achieve ~325 Wh kg^–1 single-cell energy density and 80% capacity retention after 100 cycles. Our design concept for electrolytes provides a promising path to high-energy, long-cycling Li metal batteries.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1647290

Journal Information:: Nature Energy, Journal Name: Nature Energy Journal Issue: 7 Vol. 5; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes Liu, Yayuan; Lin, Dingchang; Yuen, Pak Yan Advanced Materials, Vol. 29, Issue 10 https://doi.org/10.1002/adma.201605531	journal	December 2016
High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes Chen, Shuru; Zheng, Jianming; Mei, Donghai Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706102	journal	March 2018
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
Crosslinked Poly(tetrahydrofuran) as a Loosely Coordinating Polymer Electrolyte Mackanic, David G.; Michaels, Wesley; Lee, Minah Advanced Energy Materials, Vol. 8, Issue 25 https://doi.org/10.1002/aenm.201800703	journal	July 2018
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
Anode‐Free Full Cells: A Pathway to High‐Energy Density Lithium‐Metal Batteries Nanda, Sanjay; Gupta, Abhay; Manthiram, Arumugam Advanced Energy Materials https://doi.org/10.1002/aenm.202000804	journal	May 2020
Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes Aspern, N.; Röschenthaler, G. ‐V.; Winter, M. Angewandte Chemie International Edition, Vol. 58, Issue 45 https://doi.org/10.1002/anie.201901381	journal	November 2019
MDAnalysis: A toolkit for the analysis of molecular dynamics simulations Michaud-Agrawal, Naveen; Denning, Elizabeth J.; Woolf, Thomas B. Journal of Computational Chemistry, Vol. 32, Issue 10 https://doi.org/10.1002/jcc.21787	journal	April 2011
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
Advancing Lithium Metal Batteries Liu, Bin; Zhang, Ji-Guang; Xu, Wu Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.03.008	journal	May 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
Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy Li, Yuzhang; Huang, William; Li, Yanbin Joule, Vol. 2, Issue 10 https://doi.org/10.1016/j.joule.2018.08.004	journal	October 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
High-Efficiency Lithium-Metal Anode Enabled by Liquefied Gas Electrolytes Yang, Yangyuchen; Davies, Daniel M.; Yin, Yijie Joule, Vol. 3, Issue 8 https://doi.org/10.1016/j.joule.2019.06.008	journal	August 2019
A Dynamic, Electrolyte-Blocking, and Single-Ion-Conductive Network for Stable Lithium-Metal Anodes Yu, Zhiao; Mackanic, David G.; Michaels, Wesley Joule, Vol. 3, Issue 11 https://doi.org/10.1016/j.joule.2019.07.025	journal	November 2019
Fluorinated Solid-Electrolyte Interphase in High-Voltage Lithium Metal Batteries Li, Tao; Zhang, Xue-Qiang; Shi, Peng Joule, Vol. 3, Issue 11 https://doi.org/10.1016/j.joule.2019.09.022	journal	November 2019
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers Abraham, Mark James; Murtola, Teemu; Schulz, Roland SoftwareX, Vol. 1-2 https://doi.org/10.1016/j.softx.2015.06.001	journal	September 2015
Resolving Nanoscopic and Mesoscopic Heterogeneity of Fluorinated Species in Battery Solid-Electrolyte Interphases by Cryogenic Electron Microscopy Huang, William; Wang, Hansen; Boyle, David T. ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00194	journal	March 2020
High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries Ren, Xiaodi; Zou, Lianfeng; Jiao, Shuhong ACS Energy Letters, Vol. 4, Issue 4 https://doi.org/10.1021/acsenergylett.9b00381	journal	March 2019
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
Development of OPLS-AA Force Field Parameters for 68 Unique Ionic Liquids Sambasivarao, Somisetti V.; Acevedo, Orlando Journal of Chemical Theory and Computation, Vol. 5, Issue 4 https://doi.org/10.1021/ct900009a	journal	March 2009
Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells Li, Nanwen; Leng, Yongjun; Hickner, Michael A. Journal of the American Chemical Society, Vol. 135, Issue 27 https://doi.org/10.1021/ja403671u	journal	June 2013
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Organic Semiconducting Alloys with Tunable Energy Levels Dou, Jin-Hu; Yu, Zhi-Ao; Zhang, Jun Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.8b13471	journal	February 2019
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability Amanchukwu, Chibueze V.; Yu, Zhiao; Kong, Xian Journal of the American Chemical Society, Vol. 142, Issue 16 https://doi.org/10.1021/jacs.9b11056	journal	April 2020
Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids, Part 2: Importance of Solvate-Structure Stability for Electrolytes of Lithium Batteries Zhang, Ce; Yamazaki, Azusa; Murai, Junichi The Journal of Physical Chemistry C, Vol. 118, Issue 31 https://doi.org/10.1021/jp504099q	journal	July 2014
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
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
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
Stable cycling of high-voltage lithium metal batteries in ether electrolytes Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo Nature Energy, Vol. 3, Issue 9 https://doi.org/10.1038/s41560-018-0199-8	journal	July 2018
Advances and issues in developing salt-concentrated battery electrolytes Yamada, Yuki; Wang, Jianhui; Ko, Seongjae Nature Energy https://doi.org/10.1038/s41560-019-0336-z	journal	March 2019
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
High-energy lithium metal pouch cells with limited anode swelling and long stable cycles Niu, Chaojiang; Lee, Hongkyung; Chen, Shuru Nature Energy, Vol. 4, Issue 7 https://doi.org/10.1038/s41560-019-0390-6	journal	May 2019
Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy Wang, Jiangyan; Huang, William; Pei, Allen Nature Energy, Vol. 4, Issue 8 https://doi.org/10.1038/s41560-019-0413-3	journal	July 2019
Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte Weber, Rochelle; Genovese, Matthew; Louli, A. J. Nature Energy, Vol. 4, Issue 8 https://doi.org/10.1038/s41560-019-0428-9	journal	July 2019
Anode-less Zhang, Ji-Guang Nature Energy, Vol. 4, Issue 8 https://doi.org/10.1038/s41560-019-0449-4	journal	August 2019
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
All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents Fan, Xiulin; Ji, Xiao; Chen, Long Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0474-3	journal	October 2019
Battery revolution to evolution No authors listed Nature Energy, Vol. 4, Issue 11, p. 893-893 https://doi.org/10.1038/s41560-019-0503-2	journal	November 2019
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
Bridging the academic and industrial metrics for next-generation practical batteries Cao, Yuliang; Li, Matthew; Lu, Jun Nature Nanotechnology, Vol. 14, Issue 3 https://doi.org/10.1038/s41565-019-0371-8	journal	February 2019
Quantifying inactive lithium in lithium metal batteries Fang, Chengcheng; Li, Jinxing; Zhang, Minghao Nature, Vol. 572, Issue 7770 https://doi.org/10.1038/s41586-019-1481-z	journal	August 2019
Polymer electrolyte membranes based on poly(m-phenylene)s with sulfonic acid via long alkyl side chains Zhang, Xuan; Sheng, Li; Higashihara, Tomoya Polym. Chem., Vol. 4, Issue 4 https://doi.org/10.1039/C2PY20836A	journal	January 2013
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
Fluorinated electrolytes for 5 V lithium-ion battery chemistry Zhang, Zhengcheng; Hu, Libo; Wu, Huiming Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee24414h	journal	January 2013
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
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Polymeric [Li(NO ₃ )(monoglyme)] _n Henderson, Wesley A.; Brooks, Neil R.; Smyrl, William H. Acta Crystallographica Section E Structure Reports Online, Vol. 58, Issue 9 https://doi.org/10.1107/S160053680201499X	journal	August 2002
Crystal structure determination and refinement via SIR2014 Burla, Maria Cristina; Caliandro, Rocco; Carrozzini, Benedetta Journal of Applied Crystallography, Vol. 48, Issue 1 https://doi.org/10.1107/S1600576715001132	journal	January 2015
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy Li, Yuzhang; Li, Yanbin; Pei, Allen Science, Vol. 358, Issue 6362 https://doi.org/10.1126/science.aam6014	journal	October 2017
Hot Formation for Improved Low Temperature Cycling of Anode-Free Lithium Metal Batteries Genovese, Matthew; Louli, A. J.; Weber, Rochelle Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0661914jes	journal	January 2019

Similar Records

Dual-Solvent Li-Ion Solvation Enables High-Performance Li-Metal Batteries

Journal Article · Sat May 08 20:00:00 EDT 2021 · Advanced Materials · OSTI ID:1787601

Related Subjects

25 ENERGY STORAGE
batteries
electrochemistry
energy
materials for energy and catalysis

CCDC 1935863: Experimental Crystal Structure Determination Zhiao, Yu,; Hansen, Wang,; Xian, Kong, https://doi.org/10.5517/ccdc.csd.cc22zf6q The current record is supplemented by this dataset	dataset	January 2020
CCDC 1945342: Experimental Crystal Structure Determination Zhiao, Yu,; Hansen, Wang,; Xian, Kong, https://doi.org/10.5517/ccdc.csd.cc2398zp The current record is supplemented by this dataset	dataset	January 2020

Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Citation Formats

References (56)

Linked Research (2)

Similar Records

Related Subjects