High-entropy electrolytes for practical lithium metal batteries

Kim, Sang Cheol; Wang, Jingyang; Xu, Rong; Zhang, Pu; Chen, Yuelang; Huang, Zhuojun; Yang, Yufei; Yu, Zhiao; Oyakhire, Solomon T.; Zhang, Wenbo; Greenburg, Louisa C.; Kim, Mun Sek; Boyle, David T.; Sayavong, Philaphon; Ye, Yusheng; Qin, Jian; Bao, Zhenan; Cui, Yi

doi:10.1038/s41560-023-01280-1

High-entropy electrolytes for practical lithium metal batteries

Journal Article · Thu Jul 06 00:00:00 EDT 2023 · Nature Energy

DOI:https://doi.org/10.1038/s41560-023-01280-1· OSTI ID:2000066

^[1]; Wang, Jingyang ^[2]; Xu, Rong ^[2]; ^[2]; ^[2]; ^[2]; Yang, Yufei ^[2]; ^[2]; Oyakhire, Solomon T. ^[2]; ^[2]; Greenburg, Louisa C. ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[3]

Stanford Univ., CA (United States); SLAC
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)

Electrolyte engineering is crucial for improving battery performance, particularly for lithium metal batteries. Recent advances in electrolytes have greatly improved cyclability by enhancing electrochemical stability at the electrode interfaces, but concurrently achieving high ionic conductivity has remained challenging. Here we report an electrolyte design strategy for enhanced lithium metal batteries by increasing the molecular diversity in electrolytes, which essentially leads to high entropy electrolytes (HEEs). We find that in weakly solvating electrolytes, the entropy effect reduces ion clustering while preserving the characteristic anion-rich solvation structures, which is characterized by synchrotron-based X-ray scattering and molecular dynamics simulations. Electrolytes with smaller- sized clusters exhibit a 2-fold improvement in ionic conductivity compared to conventional weakly- solvating electrolytes, enabling stable cycling at high current densities up to 2C (6.2 mA cm^-2) in anode- free LiNi_0.6Mn_0.2Co_0.2 (NMC622)||Cu pouch cells. In conclusion, the efficacy of the design strategy is verified by performance improvements in three disparate weakly solvating electrolyte systems.

View Accepted Manuscript (DOE)

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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2000066

Journal Information:: Nature Energy, Journal Name: Nature Energy Journal Issue: 8 Vol. 8; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

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
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
High‐Fluorinated Electrolytes for Li–S Batteries Zheng, Jing; Ji, Guangbin; Fan, Xiulin Advanced Energy Materials, Vol. 9, Issue 16 https://doi.org/10.1002/aenm.201803774	journal	February 2019
Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small‐Angle X‐Ray Scattering Qian, Kun; Winans, Randall E.; Li, Tao Advanced Energy Materials, Vol. 11, Issue 4 https://doi.org/10.1002/aenm.202002821	journal	December 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
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
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 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
Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes Zheng, Jiaxin; Tan, Guoyu; Shan, Peng Chem, Vol. 4, Issue 12 https://doi.org/10.1016/j.chempr.2018.09.004	journal	December 2018
Solubilities of six lithium salts in five non-aqueous solvents and in a few of their binary mixtures Xin, Nan; Sun, Yanjun; He, Maogang Fluid Phase Equilibria, Vol. 461 https://doi.org/10.1016/j.fluid.2017.12.034	journal	April 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
Liquid electrolyte: The nexus of practical lithium metal batteries Wang, Hansen; Yu, Zhiao; Kong, Xian Joule, Vol. 6, Issue 3 https://doi.org/10.1016/j.joule.2021.12.018	journal	March 2022
High-entropy alloy: challenges and prospects Ye, Y. F.; Wang, Q.; Lu, J. Materials Today, Vol. 19, Issue 6 https://doi.org/10.1016/j.mattod.2015.11.026	journal	July 2016
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
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
Before Li Ion Batteries Winter, Martin; Barnett, Brian; Xu, Kang Chemical Reviews, Vol. 118, Issue 23 https://doi.org/10.1021/acs.chemrev.8b00422	journal	November 2018
Correlated Ion Transport and the Gel Phase in Room Temperature Ionic Liquids McEldrew, Michael; Goodwin, Zachary A. H.; Zhao, Hongbo The Journal of Physical Chemistry B, Vol. 125, Issue 10 https://doi.org/10.1021/acs.jpcb.0c09050	journal	March 2021
Li ⁺ Local Structure in Hydrofluoroether Diluted Li-Glyme Solvate Ionic Liquid Saito, Soshi; Watanabe, Hikari; Ueno, Kazuhide The Journal of Physical Chemistry B, Vol. 120, Issue 13 https://doi.org/10.1021/acs.jpcb.5b12354	journal	March 2016
Solid-Like Nano-Anion Cluster Constructs a Free Lithium-Ion-Conducting Superfluid Framework in a Water-in-Salt Electrolyte Tan, Pan; Yue, Jinming; Yu, Yuanxi The Journal of Physical Chemistry C, Vol. 125, Issue 22 https://doi.org/10.1021/acs.jpcc.1c01663	journal	June 2021
An X-ray Photoelectron Spectroscopy Primer for Solid Electrolyte Interphase Characterization in Lithium Metal Anodes Oyakhire, Solomon T.; Gong, Huaxin; Cui, Yi ACS Energy Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acsenergylett.2c01227	journal	July 2022
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
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046 https://doi.org/10.1021/ja412807w	journal	March 2014
Correlating Li-Ion Solvation Structures and Electrode Potential Temperature Coefficients Wang, Hansen; Kim, Sang Cheol; Rojas, Tomás Journal of the American Chemical Society, Vol. 143, Issue 5 https://doi.org/10.1021/jacs.0c10587	journal	January 2021
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
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
Evaluation and Reparametrization of the OPLS-AA Force Field for Proteins via Comparison with Accurate Quantum Chemical Calculations on Peptides ^† Kaminski, George A.; Friesner, Richard A.; Tirado-Rives, Julian The Journal of Physical Chemistry B, Vol. 105, Issue 28 https://doi.org/10.1021/jp003919d	journal	July 2001
Potential Energy Landscape of Bis(fluorosulfonyl)amide Canongia Lopes, José N.; Shimizu, Karina; Pádua, Agílio A. H. The Journal of Physical Chemistry B, Vol. 112, Issue 31 https://doi.org/10.1021/jp803309c	journal	August 2008
Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes Lin, Dingchang; Liu, Yayuan; Liang, Zheng Nature Nanotechnology, Vol. 11, Issue 7 https://doi.org/10.1038/nnano.2016.32	journal	March 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
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
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
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
Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis Louli, A. J.; Eldesoky, A.; Weber, Rochelle Nature Energy, Vol. 5, Issue 9 https://doi.org/10.1038/s41560-020-0668-8	journal	August 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
Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries Niu, Chaojiang; Liu, Dianying; Lochala, Joshua A. Nature Energy, Vol. 6, Issue 7 https://doi.org/10.1038/s41560-021-00852-3	journal	June 2021
Pressure-tailored lithium deposition and dissolution in lithium metal batteries Fang, Chengcheng; Lu, Bingyu; Pawar, Gorakh Nature Energy, Vol. 6, Issue 10 https://doi.org/10.1038/s41560-021-00917-3	journal	October 2021
High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes Zhou, Laidong; Zuo, Tong-Tong; Kwok, Chun Yuen Nature Energy, Vol. 7, Issue 1 https://doi.org/10.1038/s41560-021-00952-0	journal	January 2022
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
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries Fu, Chengyin; Venturi, Victor; Kim, Jinsoo Nature Materials, Vol. 19, Issue 7 https://doi.org/10.1038/s41563-020-0655-2	journal	April 2020
Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries Kim, Mun Sek; Zhang, Zewen; Rudnicki, Paul E. Nature Materials, Vol. 21, Issue 4 https://doi.org/10.1038/s41563-021-01172-3	journal	January 2022
High-entropy ceramics Oses, Corey; Toher, Cormac; Curtarolo, Stefano Nature Reviews Materials, Vol. 5, Issue 4 https://doi.org/10.1038/s41578-019-0170-8	journal	February 2020
Transition of lithium growth mechanisms in liquid electrolytes Bai, Peng; Li, Ju; Brushett, Fikile R. Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE01674J	journal	January 2016
Ionic association analysis of LiTDI, LiFSI and LiPF ₆ in EC/DMC for better Li-ion battery performances Berhaut, Christopher L.; Lemordant, Daniel; Porion, Patrice RSC Advances, Vol. 9, Issue 8 https://doi.org/10.1039/C8RA08430K	journal	January 2019
Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries Wang, Qingsong; Sarkar, Abhishek; Wang, Di Energy & Environmental Science, Vol. 12, Issue 8 https://doi.org/10.1039/C9EE00368A	journal	January 2019
Electrolyte design implications of ion-pairing in low-temperature Li metal batteries Holoubek, John; Kim, Kangwoon; Yin, Yijie Energy & Environmental Science, Vol. 15, Issue 4 https://doi.org/10.1039/D1EE03422G	journal	January 2022
Unifying the clustering kinetics of lithium polysulfides with the nucleation behavior of Li ₂ S in lithium–sulfur batteries Gupta, Abhay; Manthiram, Arumugam Journal of Materials Chemistry A, Vol. 9, Issue 22 https://doi.org/10.1039/D1TA02779D	journal	January 2021
The ORCA quantum chemistry program package Neese, Frank; Wennmohs, Frank; Becker, Ute The Journal of Chemical Physics, Vol. 152, Issue 22 https://doi.org/10.1063/5.0004608	journal	June 2020
Theory of ion aggregation and gelation in super-concentrated electrolytes McEldrew, Michael; Goodwin, Zachary A. H.; Bi, Sheng The Journal of Chemical Physics, Vol. 152, Issue 23 https://doi.org/10.1063/5.0006197	journal	June 2020
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
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
Morphology of ion clusters in aqueous electrolytes Hassan, Sergio A. Physical Review E, Vol. 77, Issue 3 https://doi.org/10.1103/PhysRevE.77.031501	journal	March 2008
Electrical Energy Storage and Intercalation Chemistry Whittingham, M. S. Science, Vol. 192, Issue 4244 https://doi.org/10.1126/science.192.4244.1126	journal	June 1976
How lithium dendrites form in liquid batteries Xiao, Jie Science, Vol. 366, Issue 6464 https://doi.org/10.1126/science.aay8672	journal	October 2019
High-entropy mechanism to boost ionic conductivity Zeng, Yan; Ouyang, Bin; Liu, Jue Science, Vol. 378, Issue 6626 https://doi.org/10.1126/science.abq1346	journal	December 2022
Exploring the Impact of Mechanical Pressure on the Performance of Anode-Free Lithium Metal Cells Louli, A. J.; Genovese, Matthew; Weber, Rochelle Journal of The Electrochemical Society, Vol. 166, Issue 8 https://doi.org/10.1149/2.0091908jes	journal	January 2019
Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF ₆ in EC:DEC Lundgren, Henrik; Behm, Mårten; Lindbergh, Göran Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0641503jes	journal	December 2014
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