Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery

Chen, Yuelang; Yu, Zhiao; Rudnicki, Paul; Gong, Huaxin; Huang, Zhuojun; Kim, Sang Cheol; Lai, Jian-Cheng; Kong, Xian; Qin, Jian; Cui, Yi; Bao, Zhenan

doi:10.1021/jacs.1c09006

Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery

Journal Article · Thu Oct 28 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c09006· OSTI ID:1878520

^[1]; ^[1]; Rudnicki, Paul ^[1]; ^[1]; ^[1]; ^[1]; Lai, Jian-Cheng ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Stanford Univ., CA (United States)

1,2-Dimethoxyethane (DME) is a common electrolyte solvent for lithium metal batteries. Various DME-based electrolyte designs have improved long-term cyclability of high-voltage full cells. However, insufficient Coulombic efficiency at the Li anode and poor high-voltage stability remain a challenge for DME electrolytes. Here, we report a molecular design principle that utilizes a steric hindrance effect to tune the solvation structures of Li⁺ ions. In this work, we hypothesized that by substituting the methoxy groups on DME with larger-sized ethoxy groups, the resulting 1,2-diethoxyethane (DEE) should have a weaker solvation ability and consequently more anion-rich inner solvation shells, both of which enhance interfacial stability at the cathode and anode. Experimental and computational evidence indicates such steric-effect-based design leads to an appreciable improvement in electrochemical stability of lithium bis(fluorosulfonyl)imide (LiFSI)/DEE electrolytes. Under stringent full-cell conditions of 4.8 mAh cm^–2 NMC811, 50 μm thin Li, and high cutoff voltage at 4.4 V, 4 M LiFSI/DEE enabled 182 cycles until 80% capacity retention while 4 M LiFSI/DME only achieved 94 cycles. This work points out a promising path toward the molecular design of non-fluorinated ether-based electrolyte solvents for practical high-voltage 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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1878520

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Anode-Free Rechargeable Lithium Metal Batteries Qian, Jiangfeng; Adams, Brian D.; Zheng, Jianming Advanced Functional Materials, Vol. 26, Issue 39 https://doi.org/10.1002/adfm.201602353	journal	August 2016
Fluorobenzene, A Low‐Density, Economical, and Bifunctional Hydrocarbon Cosolvent for Practical Lithium Metal Batteries Jiang, Zhipeng; Zeng, Ziqi; Liang, Xinmiao Advanced Functional Materials, Vol. 31, Issue 1 https://doi.org/10.1002/adfm.202005991	journal	September 2020
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
Nonpolar Alkanes Modify Lithium‐Ion Solvation for Improved Lithium Deposition and Stripping Amanchukwu, Chibueze V.; Kong, Xian; Qin, Jian Advanced Energy Materials, Vol. 9, Issue 41 https://doi.org/10.1002/aenm.201902116	journal	September 2019
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
Corrosion Prevention Mechanism of Aluminum Metal in Superconcentrated Electrolytes Yamada, Yuki; Chiang, Ching Hua; Sodeyama, Keitaro ChemElectroChem, Vol. 2, Issue 11 https://doi.org/10.1002/celc.201500235	journal	July 2015
Gabedit-A graphical user interface for computational chemistry softwares Allouche, Abdul-Rahman Journal of Computational Chemistry, Vol. 32, Issue 1 https://doi.org/10.1002/jcc.21600	journal	November 2010
An Aggregate Cluster-Dispersed Electrolyte Guides the Uniform Nucleation and Growth of Lithium at Lithium Metal Anodes Lee, Min-Suk; Roev, Victor; Jung, Changhoon ChemistrySelect, Vol. 3, Issue 41 https://doi.org/10.1002/slct.201800757	journal	November 2018
Simultaneous Stabilization of the Solid/Cathode Electrolyte Interface in Lithium Metal Batteries by a New Weakly Solvating Electrolyte Pham, Thuy Duong; Lee, Kyung‐Koo Small, Vol. 17, Issue 20 https://doi.org/10.1002/smll.202100133	journal	April 2021
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries Aurbach, Doron Journal of Power Sources, Vol. 89, Issue 2 https://doi.org/10.1016/S0378-7753(00)00431-6	journal	August 2000
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
Liquid electrolyte based on lithium bis-fluorosulfonyl imide salt: Aluminum corrosion studies and lithium ion battery investigations Abouimrane, A.; Ding, J.; Davidson, I. J. Journal of Power Sources, Vol. 189, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.08.077	journal	April 2009
Suppression of aluminum corrosion by using high concentration LiTFSI electrolyte Matsumoto, Kazuaki; Inoue, Kazuhiko; Nakahara, Kentaro Journal of Power Sources, Vol. 231 https://doi.org/10.1016/j.jpowsour.2012.12.028	journal	June 2013
Electrolyte design for Li metal-free Li batteries Chen, Ji; Li, Qin; Pollard, Travis P. Materials Today https://doi.org/10.1016/j.mattod.2020.04.004	journal	April 2020
Ultrahigh coulombic efficiency electrolyte enables Li\|\|SPAN batteries with superior cycling performance Liu, Haodong; Holoubek, John; Zhou, Hongyao Materials Today, Vol. 42 https://doi.org/10.1016/j.mattod.2020.09.035	journal	January 2021
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
Localized High Concentration Electrolytes for High Voltage Lithium–Metal Batteries: Correlation between the Electrolyte Composition and Its Reductive/Oxidative Stability Perez Beltran, Saul; Cao, Xia; Zhang, Ji-Guang Chemistry of Materials, Vol. 32, Issue 14 https://doi.org/10.1021/acs.chemmater.0c00987	journal	July 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
New Concepts in Electrolytes Li, Matthew; Wang, Chunsheng; Chen, Zhongwei Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00531	journal	February 2020
Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries Ma, Tianyuan; Xu, Gui-Liang; Li, Yan The Journal of Physical Chemistry Letters, Vol. 8, Issue 5 https://doi.org/10.1021/acs.jpclett.6b02933	journal	February 2017
Long-Term Stable Lithium Metal Anode in Highly Concentrated Sulfolane-Based Electrolytes with Ultrafine Porous Polyimide Separator Maeyoshi, Yuta; Ding, Dong; Kubota, Masaaki ACS Applied Materials & Interfaces, Vol. 11, Issue 29 https://doi.org/10.1021/acsami.9b05257	journal	June 2019
Efficient Lithium Metal Cycling over a Wide Range of Pressures from an Anion-Derived Solid-Electrolyte Interphase Framework Wang, Hansen; Huang, William; Yu, Zhiao ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02533	journal	February 2021
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
Transport in Superconcentrated LiPF ₆ and LiBF ₄ /Propylene Carbonate Electrolytes Self, Julian; Fong, Kara D.; Persson, Kristin A. ACS Energy Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsenergylett.9b02118	journal	October 2019
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Oxidative-Stability Enhancement and Charge Transport Mechanism in Glyme–Lithium Salt Equimolar Complexes Yoshida, Kazuki; Nakamura, Megumi; Kazue, Yuichi Journal of the American Chemical Society, Vol. 133, Issue 33, p. 13121-13129 https://doi.org/10.1021/ja203983r	journal	August 2011
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
Potentiometric Measurement to Probe Solvation Energy and Its Correlation to Lithium Battery Cyclability Kim, Sang Cheol; Kong, Xian; Vilá, Rafael A. Journal of the American Chemical Society, Vol. 143, Issue 27 https://doi.org/10.1021/jacs.1c03868	journal	June 2021
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
Micromorphological Studies of Lithium Electrodes in Alkyl Carbonate Solutions Using in Situ Atomic Force Microscopy Cohen, Yaron S.; Cohen, Yair; Aurbach, Doron The Journal of Physical Chemistry B, Vol. 104, Issue 51 https://doi.org/10.1021/jp002526b	journal	December 2000
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
Design principles for electrolytes and interfaces for stable lithium-metal batteries Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.114	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
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Passivation behaviour of aluminium current collector in ionic liquid alkyl carbonate (hybrid) electrolytes Theivaprakasam, Sowmiya; Girard, Gaetan; Howlett, Patrick npj Materials Degradation, Vol. 2, Issue 1 https://doi.org/10.1038/s41529-018-0033-6	journal	March 2018
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
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
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
Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries Chen, Ji; Fan, Xiulin; Li, Qin Nature Energy, Vol. 5, Issue 5 https://doi.org/10.1038/s41560-020-0601-1	journal	April 2020
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
Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature Holoubek, John; Liu, Haodong; Wu, Zhaohui Nature Energy, Vol. 6, Issue 3 https://doi.org/10.1038/s41560-021-00783-z	journal	February 2021
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
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
Concentrated electrolytes: decrypting electrolyte properties and reassessing Al corrosion mechanisms McOwen, Dennis W.; Seo, Daniel M.; Borodin, Oleg Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42351D	journal	January 2014
Guidelines to design organic electrolytes for lithium-ion batteries: environmental impact, physicochemical and electrochemical properties Flamme, Benjamin; Rodriguez Garcia, Gonzalo; Weil, Marcel Green Chemistry, Vol. 19, Issue 8 https://doi.org/10.1039/C7GC00252A	journal	January 2017
Enhancing metallic lithium battery performance by tuning the electrolyte solution structure Huang, Feifei; Ma, Guoqiang; Wen, Zhaoyin Journal of Materials Chemistry A, Vol. 6, Issue 4 https://doi.org/10.1039/C7TA08274F	journal	January 2018
Concentrated mixed cation acetate “water-in-salt” solutions as green and low-cost high voltage electrolytes for aqueous batteries Lukatskaya, Maria R.; Feldblyum, Jeremy I.; Mackanic, David G. Energy & Environmental Science, Vol. 11, Issue 10 https://doi.org/10.1039/C8EE00833G	journal	January 2018
Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes Alvarado, Judith; Schroeder, Marshall A.; Pollard, Travis P. Energy & Environmental Science, Vol. 12, Issue 2 https://doi.org/10.1039/C8EE02601G	journal	January 2019
Accounting for electronic polarization in non-polarizable force fields Leontyev, Igor; Stuchebrukhov, Alexei Physical Chemistry Chemical Physics, Vol. 13, Issue 7 https://doi.org/10.1039/c0cp01971b	journal	January 2011
A superconcentrated ether electrolyte for fast-charging Li-ion batteries Yamada, Yuki; Yaegashi, Makoto; Abe, Takeshi Chemical Communications, Vol. 49, Issue 95, p. 11194-11196 https://doi.org/10.1039/c3cc46665e	journal	January 2013
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
LigParGen web server: an automatic OPLS-AA parameter generator for organic ligands Dodda, Leela S.; Cabeza de Vaca, Israel; Tirado-Rives, Julian Nucleic Acids Research, Vol. 45, Issue W1 https://doi.org/10.1093/nar/gkx312	journal	April 2017
Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B. Journal of The Electrochemical Society, Vol. 151, Issue 2 https://doi.org/10.1149/1.1635384	journal	January 2004
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
Review—SEI: Past, Present and Future Peled, E.; Menkin, S. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.1441707jes	journal	January 2017
Formation of Al2O3 Film and AlF3 Containing Al2O3 Film by an Anodic Polarization of Aluminum in Ionic Liquids Tateishi, Kazuyuki; Waki, Akiko; Ogino, Hiroyuki Electrochemistry, Vol. 80, Issue 8 https://doi.org/10.5796/electrochemistry.80.556	journal	January 2012

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