Localized high-concentration electrolytes get more localized through micelle-like structures

Efaw, Corey M.; Wu, Qisheng; Gao, Ningshengjie; Zhang, Yugang; Zhu, Haoyu; Gering, Kevin; Hurley, Michael F.; Xiong, Hui; Hu, Enyuan; Cao, Xia; Xu, Wu; Zhang, Ji-Guang; Dufek, Eric J.; Xiao, Jie; Yang, Xiao-Qing; Liu, Jun; Qi, Yue; Li, Bin

doi:10.1038/s41563-023-01700-3

Title: Localized high-concentration electrolytes get more localized through micelle-like structures

Journal Article · 05 November 2023 · Nature Materials

DOI: https://doi.org/10.1038/s41563-023-01700-3 · OSTI ID:2205647

^[1];

^[2];

^[3];

^[4]; Zhu, Haoyu ^[5]; Gering, Kevin ^[3]; Hurley, Michael F. ^[5];

^[5];

^[6];

^[7];

^[3];

^[7];

^[6];

^[7];

^[2];

^[8]

Idaho National Laboratory (INL), Idaho Falls, ID (United States); Boise State Univ., ID (United States)
Brown Univ., Providence, RI (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Boise State Univ., ID (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States); Boise State Univ., ID (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media despite having a complex chemical composition and atomistic solvation structures, leaving a knowledge gap of the microstructural characteristics. Here, we reveal a unique micelle-like structure in a localized high-concentration electrolyte, in which the solvent acts as a surfactant between an insoluble salt in a diluent. The miscibility of the solvent with the diluent and simultaneous solubility of the salt results in a micelle-like structure with a smeared interface and an increased salt concentration at the centre of the salt–solvent clusters that extends the salt solubility. These intermingling miscibility effects have temperature dependencies, wherein a typical localized high-concentration electrolyte peaks in localized cluster salt concentration near room temperature and is used to form a stable solid–electrolyte interphase on a Li metal anode. Importantly, these findings serve as a guide to predicting a stable ternary phase diagram and connecting the electrolyte microstructure with electrolyte formulation and formation protocols of solid–electrolyte interphases for enhanced battery cyclability.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Idaho National Laboratory (INL), Idaho Falls, ID (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: SC0012704; AC07-05ID14517

OSTI ID:: 2205647

Alternate ID(s):: OSTI ID: 2328511; OSTI ID: 2386883; OSTI ID: 2251586

Report Number(s):: BNL--224993-2023-JAAM

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 12 Vol. 22; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Universal Solvation Model Based on the Generalized Born Approximation with Asymmetric Descreening Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 5, Issue 9 https://doi.org/10.1021/ct900312z	journal	August 2009
Superconcentrated electrolytes for a high-voltage lithium-ion battery Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12032	journal	June 2016
Solvent–Diluent Interaction-Mediated Solvation Structure of Localized High-Concentration Electrolytes Ren, Feihong; Li, Zhendong; Chen, Jiahe ACS Applied Materials & Interfaces, Vol. 14, Issue 3 https://doi.org/10.1021/acsami.1c21638	journal	January 2022
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
A lightweight localized high-concentration ether electrolyte for high-voltage Li-Ion and Li-metal batteries Peng, Xudong; Lin, Yanke; Wang, Yu Nano Energy, Vol. 96 https://doi.org/10.1016/j.nanoen.2022.107102	journal	June 2022
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry Borodin, Oleg; Olguin, Marco; Ganesh, P. Physical Chemistry Chemical Physics, Vol. 18, Issue 1 https://doi.org/10.1039/C5CP05121E	journal	January 2016
Review—Superconcentrated Electrolytes for Lithium Batteries Yamada, Yuki; Yamada, Atsuo Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0041514jes	journal	January 2015
Molecular simulations of electrolyte structure and dynamics in lithium–sulfur battery solvents Park, Chanbum; Kanduč, Matej; Chudoba, Richard Journal of Power Sources, Vol. 373 https://doi.org/10.1016/j.jpowsour.2017.10.081	journal	January 2018
Emerging Era of Electrolyte Solvation Structure and Interfacial Model in Batteries Cheng, Haoran; Sun, Qujiang; Li, Leilei ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02425	journal	January 2022
A Comparative Study of the Determination of the Critical Micelle Concentration by Conductivity and Dielectric Constant Measurements Pérez-Rodríguez, Martín; Prieto, Gerardo; Rega, Carlos Langmuir, Vol. 14, Issue 16 https://doi.org/10.1021/la980296a	journal	July 1998
Nanoemulsions versus microemulsions: terminology, differences, and similarities McClements, David Julian Soft Matter, Vol. 8, Issue 6 https://doi.org/10.1039/C2SM06903B	journal	January 2012
Thermal stability and decomposition of lithium bis(fluorosulfonyl)imide (LiFSI) salts Kerner, Manfred; Plylahan, Nareerat; Scheers, Johan RSC Advances, Vol. 6, Issue 28 https://doi.org/10.1039/C5RA25048J	journal	January 2016
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
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
Controlling Ion Coordination Structure and Diffusion Kinetics for Optimized Electrode-Electrolyte Interphases and High-Performance Si Anodes Jia, Haiping; Gao, Peiyuan; Zou, Lianfeng Chemistry of Materials, Vol. 32, Issue 20 https://doi.org/10.1021/acs.chemmater.0c02954	journal	September 2020
Preferential Solvation of Li+ Directs Formation of Interphase on Graphitic Anode von Cresce, Arthur; Xu, Kang Electrochemical and Solid-State Letters, Vol. 14, Issue 10 https://doi.org/10.1149/1.3615828	journal	January 2011
COMPASS III: automated fitting workflows and extension to ionic liquids Akkermans, Reinier L. C.; Spenley, Neil A.; Robertson, Struan H. Molecular Simulation, Vol. 47, Issue 7 https://doi.org/10.1080/08927022.2020.1808215	journal	August 2020
Molecular dynamics with coupling to an external bath Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F. The Journal of Chemical Physics, Vol. 81, Issue 8 https://doi.org/10.1063/1.448118	journal	October 1984
Structural regulation chemistry of lithium ion solvation for lithium batteries Wang, Zhongsheng; Wang, Huaping; Qi, Shihan EcoMat, Vol. 4, Issue 4 https://doi.org/10.1002/eom2.12200	journal	March 2022
Uncovering the Solvation Structure of LiPF ₆ ‐Based Localized Saturated Electrolytes and Their Effect on LiNiO ₂ ‐Based Lithium‐Metal Batteries Su, Laisuo; Zhao, Xunhua; Yi, Michael Advanced Energy Materials https://doi.org/10.1002/aenm.202201911	journal	August 2022
FT-Raman spectroscopy study of solvent-in-salt electrolytes Suo, Liumin; Zheng, Fang; Hu, Yong-Sheng Chinese Physics B, Vol. 25, Issue 1 https://doi.org/10.1088/1674-1056/25/1/016101	journal	January 2016
Countersolvent Electrolytes for Lithium‐Metal Batteries Piao, Nan; Ji, Xiao; Xu, Hong Advanced Energy Materials, Vol. 10, Issue 10 https://doi.org/10.1002/aenm.201903568	journal	March 2020
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
Pursuing graphite-based K-ion O₂ batteries: a lesson from Li-ion batteries Qin, Lei; Zhang, Songwei; Zheng, Jingfeng Energy & Environmental Science, Vol. 13, Issue 10 https://doi.org/10.1039/D0EE01361G	journal	January 2020
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
Ionic liquids effect on critical micelle concentration of SDS: Conductivity, fluorescence and NMR studies Pal, Amalendu; Chaudhary, Sheena Fluid Phase Equilibria, Vol. 372 https://doi.org/10.1016/j.fluid.2014.03.024	journal	June 2014
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
Solvation and Dynamics of Sodium and Potassium in Ethylene Carbonate from ab Initio Molecular Dynamics Simulations Pham, Tuan Anh; Kweon, Kyoung E.; Samanta, Amit The Journal of Physical Chemistry C, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpcc.7b06457	journal	September 2017
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries Suo, Liumin; Hu, Yong-Sheng; Li, Hong Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2513	journal	February 2013
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
Effect of the Electric Double Layer (EDL) in Multicomponent Electrolyte Reduction and Solid Electrolyte Interphase (SEI) Formation in Lithium Batteries Wu, Qisheng; McDowell, Matthew T.; Qi, Yue Journal of the American Chemical Society, Vol. 145, Issue 4 https://doi.org/10.1021/jacs.2c11807	journal	January 2023
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
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
Quantum Chemistry and Molecular Dynamics Simulation Study of Dimethyl Carbonate: Ethylene Carbonate Electrolytes Doped with LiPF ₆ Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 113, Issue 6 https://doi.org/10.1021/jp809614h	journal	February 2009
Density Functional Study of the Conformations and Vibrations of 1,2-Dimethoxyethane Yoshida, Hiroshi; Matsuura, Hiroatsu The Journal of Physical Chemistry A, Vol. 102, Issue 16 https://doi.org/10.1021/jp9800766	journal	March 1998
Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids Toxvaerd, Søren; Dyre, Jeppe C. The Journal of Chemical Physics, Vol. 135, Issue 13 https://doi.org/10.1063/1.3643123	journal	October 2011
Solvating power series of electrolyte solvents for lithium batteries Su, Chi-Cheung; He, Meinan; Amine, Rachid Energy & Environmental Science, Vol. 12, Issue 4 https://doi.org/10.1039/C9EE00141G	journal	January 2019
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
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
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
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
Stabilized Rechargeable Aqueous Zinc Batteries Using Ethylene Glycol as Water Blocker Wang, Nan; Yang, Yang; Qiu, Xuan ChemSusChem, Vol. 13, Issue 20 https://doi.org/10.1002/cssc.202001750	journal	August 2020
At the polymer electrolyte interfaces: the role of the polymer host in interphase layer formation in Li-batteries Sun, Bing; Xu, Chao; Mindemark, Jonas Journal of Materials Chemistry A, Vol. 3, Issue 26 https://doi.org/10.1039/C5TA02485D	journal	January 2015
Dielectric constants of acetonitrile, ?-butyrolactone, propylene carbonate, and 1,2-dimethoxyethane as a function of pressure and temperature C�t�, Jean-Fran�ois; Brouillette, Dany; Desnoyers, Jacques E. Journal of Solution Chemistry, Vol. 25, Issue 12 https://doi.org/10.1007/BF00972644	journal	December 1996
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
Highly reversible zinc metal anodes enabled by a three-dimensional silver host for aqueous batteries Xue, Ruifang; Kong, Jingyi; Wu, Ying Journal of Materials Chemistry A, Vol. 10, Issue 18 https://doi.org/10.1039/D2TA00326K	journal	January 2022
A Micelle Electrolyte Enabled by Fluorinated Ether Additives for Polysulfide Suppression and Li Metal Stabilization in Li-S Battery Zhao, Yangzhi; Fang, Chen; Zhang, Guangzhao Frontiers in Chemistry, Vol. 8 https://doi.org/10.3389/fchem.2020.00484	journal	June 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
Enhanced Sodium Metal/Electrolyte Interface by a Localized High-Concentration Electrolyte for Sodium Metal Batteries: First-Principles Calculations and Experimental Studies Wang, Yueda; Jiang, Rui; Liu, Yongchao ACS Applied Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1021/acsaem.1c01573	journal	July 2021
Robust Solid Electrolyte Interphases in Localized High Concentration Electrolytes Boosting Black Phosphorus Anode for Potassium-Ion Batteries Du, Xiaoqiong; Zhang, Biao ACS Nano, Vol. 15, Issue 10 https://doi.org/10.1021/acsnano.1c07414	journal	October 2021
Stable Anion‐Derived Solid Electrolyte Interphase in Lithium Metal Batteries Li, Tao; Zhang, Xue‐Qiang; Yao, Nan Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/anie.202107732	journal	September 2021

Similar Records

Localized High-Concentration Electrolytes Get More Localized

Conference · 2023 · OSTI ID:1986462

Efaw, Corey Michael; Wu, Qisheng; Gao, Ningshengjie; +5 more

Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface

Journal Article · 2019 · Journal of Materials Chemistry A · OSTI ID:1574904

Zheng, Yu; Soto, Fernando A.; Ponce, Victor; +4 more

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries

Journal Article · 2021 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1767364

Cao, Xia; Gao, Peiyuan; Ren, Xiaodi; +12 more

Related Subjects

25 ENERGY STORAGE
electrolyte
low temperature
high voltage
lithium-ion battery
batteries
molecular dynamics

Title: Localized high-concentration electrolytes get more localized through micelle-like structures

Citation Formats

References (52)

Similar Records

Related Subjects