Formation of Larger Solvation Shells in a LiFSI Salt Solution for Enhanced Li+ Transport

Osti, Naresh C.; Mamontov, Eugene

doi:10.1021/acs.jpclett.5c02445

Formation of Larger Solvation Shells in a LiFSI Salt Solution for Enhanced Li⁺ Transport

Journal Article · Wed Oct 01 00:00:00 EDT 2025 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5c02445· OSTI ID:3002273

^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Electrodes and electrolytes in Li-ion batteries (LIBs) are crucial for their electrochemical performance, and fabricating these materials to achieve the desired properties for improved efficiency is challenging. A recent study published in Nature ( Nature 2024, 627, 101−107) outlined guidelines for designing an electrolyte using fluoroacetonitrile (FACN), a small-molecule solvent with low solvation energy. This characteristic enables the formation of an anion-rich inorganic interphase in a 1.3 M lithium bis(fluorosulfonyl)imide (LiFSI) solution, facilitating higher ionic conductivity, even at low temperatures. The formation of a ligand channel was postulated and demonstrated in the simulation due to the attraction of small solvent molecules from the secondary solvation shell to the Li⁺ ion in the primary solvation shell, thereby enhancing Li⁺ transport. While that study primarily focused on Li⁺ ion behavior in LIBs, the behavior of FACN in solutions with different lithium salts and what makes LiFSI in FACN outperform other systems remain to be explored. In conclusion, using an experimental technique sensitive to FACN molecules, here we directly observe formation of larger solvation shells in a LiFSI solution compared to the Li salts with different anions, consistent with the postulated ligand-channel-mechanism and potentially paving the way to achieving enhanced ionic conductivity and energy density during LIB operation.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 3002273

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 40 Vol. 16; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (27)

Uncharted Waters: Super-Concentrated Electrolytes Borodin, Oleg; Self, Julian; Persson, Kristin A. Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.12.007	journal	January 2020
Anticatalytic Strategies to Suppress Water Electrolysis in Aqueous Batteries Sui, Yiming; Ji, Xiulei Chemical Reviews, Vol. 121, Issue 11 https://doi.org/10.1021/acs.chemrev.1c00191	journal	April 2021
Application of Ionic Liquids to Energy Storage and Conversion Materials and Devices Watanabe, Masayoshi; Thomas, Morgan L.; Zhang, Shiguo Chemical Reviews, Vol. 117, Issue 10 https://doi.org/10.1021/acs.chemrev.6b00504	journal	January 2017
Scalable Screening of Soft Matter: A Case Study of Mixtures of Ionic Liquids and Organic Solvents Thompson, Matthew W.; Matsumoto, Ray; Sacci, Robert L. The Journal of Physical Chemistry B, Vol. 123, Issue 6 https://doi.org/10.1021/acs.jpcb.8b11527	journal	January 2019
Molecular Structure, Chemical Exchange, and Conductivity Mechanism of High Concentration LiTFSI Electrolytes Galle Kankanamge, Susith R.; Kuroda, Daniel G. The Journal of Physical Chemistry B, Vol. 124, Issue 10 https://doi.org/10.1021/acs.jpcb.9b10795	journal	February 2020
Anion Solvation in Carbonate-Based Electrolytes von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg The Journal of Physical Chemistry C, Vol. 119, Issue 49 https://doi.org/10.1021/acs.jpcc.5b08895	journal	November 2015
Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris The Journal of Physical Chemistry C, Vol. 122, Issue 19 https://doi.org/10.1021/acs.jpcc.8b02521	journal	April 2018
Revealing the Solvation Structure and Dynamics of Carbonate Electrolytes in Lithium-Ion Batteries by Two-Dimensional Infrared Spectrum Modeling Liang, Chungwen; Kwak, Kyungwon; Cho, Minhaeng The Journal of Physical Chemistry Letters, Vol. 8, Issue 23 https://doi.org/10.1021/acs.jpclett.7b02623	journal	November 2017
Solvation Structures in Electrolyte and the Interfacial Chemistry for Na-Ion Batteries Hu, Yong-Sheng; Pan, Huilin ACS Energy Letters, Vol. 7, Issue 12 https://doi.org/10.1021/acsenergylett.2c02529	journal	December 2022
Weakening Ionic Coordination for High Ionic Conductivity Composite Solid Electrolytes Yu, Xiangnan; Zhao, Liang; Li, Yuhang ACS Energy Letters, Vol. 9, Issue 5 https://doi.org/10.1021/acsenergylett.4c00636	journal	April 2024
High-Entropy Electrolytes for Lithium-Ion Batteries Wang, Qidi; Wang, Jianlin; Heringa, Jouke R. ACS Energy Letters, Vol. 9, Issue 8 https://doi.org/10.1021/acsenergylett.4c01358	journal	July 2024
Imidazolium-Based Ionic Liquid Electrolytes for Fluoride Ion Batteries Alshangiti, Omar; Galatolo, Giulia; Di Mino, Camilla ACS Energy Letters, Vol. 9, Issue 12 https://doi.org/10.1021/acsenergylett.4c02663	journal	November 2024
Methylsulfonylmethane-Based Deep Eutectic Solvent as a New Type of Green Electrolyte for a High-Energy-Density Aqueous Lithium-Ion Battery Jiang, Ping; Chen, Liang; Shao, Hezhu ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00968	journal	May 2019
Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes Borodin, Oleg; Suo, Liumin; Gobet, Mallory ACS Nano, Vol. 11, Issue 10 https://doi.org/10.1021/acsnano.7b05664	journal	October 2017
Electrode Degradation in Lithium-Ion Batteries Pender, Joshua P.; Jha, Gaurav; Youn, Duck Hyun ACS Nano, Vol. 14, Issue 2 https://doi.org/10.1021/acsnano.9b04365	journal	January 2020
Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems Simon, P.; Gogotsi, Y. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar200306b	journal	June 2012
The role of concentration in electrolyte solutions for non-aqueous lithium-based batteries Giffin, Guinevere A. Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32794-z	journal	September 2022
Influences from solvents on charge storage in titanium carbide MXenes Wang, Xuehang; Mathis, Tyler S.; Li, Ke Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0339-9	journal	March 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
Ligand-channel-enabled ultrafast Li-ion conduction Lu, Di; Li, Ruhong; Rahman, Muhammad Mominur Nature, Vol. 627, Issue 8002 https://doi.org/10.1038/s41586-024-07045-4	journal	February 2024
Tailored Li-ion battery electrodes and electrolytes for extreme condition operations Jeong, Daecheol; Tackett, Brian M.; Pol, Vilas G. Communications Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/s42004-025-01564-5	journal	June 2025
Ionic liquid-based green processes for energy production Zhang, Suojiang; Sun, Jian; Zhang, Xiaochun Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60409H	journal	January 2014
Microscopic dynamics in room-temperature ionic liquids confined in materials for supercapacitor applications Osti, Naresh C.; Mamontov, Eugene Sustainable Energy & Fuels, Vol. 4, Issue 4 https://doi.org/10.1039/C9SE00829B	journal	January 2020
Backscattering silicon spectrometer (BASIS): sixteen years in advanced materials characterization Osti, Naresh C.; Jalarvo, Niina; Mamontov, Eugene Materials Horizons, Vol. 11, Issue 19 https://doi.org/10.1039/D4MH00690A	journal	January 2024
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS Mamontov, E.; Herwig, K. W. Review of Scientific Instruments, Vol. 82, Issue 8 https://doi.org/10.1063/1.3626214	journal	August 2011
Exploring solvation structure and transport behavior for rational design of advanced electrolytes for next generation of lithium batteries Liu, Xiaozhao; Koverga, Volodymyr; Nguyen, Hoai T. Applied Physics Reviews, Vol. 11, Issue 2 https://doi.org/10.1063/5.0187154	journal	April 2024
Designing better electrolytes Meng, Y. Shirley; Srinivasan, Venkat; Xu, Kang Science, Vol. 378, Issue 6624 https://doi.org/10.1126/science.abq3750	journal	December 2022

Similar Records

Electrolyte Solvation and Ionic Association. V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures

Journal Article · Tue Sep 30 00:00:00 EDT 2014 · Journal of the Electrochemical Society, 161(14):A2042-A2053 · OSTI ID:1167619

Ion Pairing, Clustering and Transport in a LiFSI-TMP Electrolyte as Functions of Salt Concentration using Molecular Dynamics Simulations

Journal Article · Mon Apr 05 20:00:00 EDT 2021 · Journal of the Electrochemical Society · OSTI ID:1838938

Electrolyte Solvation and Ionic Association: Part IX. Structures and Raman Spectroscopic Characterization of LiFSI Solvates

Journal Article · Sun Nov 27 19:00:00 EST 2022 · Journal of the Electrochemical Society · OSTI ID:2419630

Related Subjects

Batteries
Electrolytes
Salts
Solvation
Solvents

Formation of Larger Solvation Shells in a LiFSI Salt Solution for Enhanced Li+ Transport

Citation Formats

References (27)

Similar Records

Related Subjects

Formation of Larger Solvation Shells in a LiFSI Salt Solution for Enhanced Li⁺ Transport