Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent's Mole Fraction

Naresh C. Osti; Bishnu Prasad Thapaliya; Ray A. Matsumoto; Arjun Bansal; Xiaobo Lin; Peter T. Cummings; Madhusudan Tyagi; Sheng Dai; Eugene Mamontov

doi:10.1021/acs.jpclett.2c00487

Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent's Mole Fraction

Naresh C. Osti, Bishnu Prasad Thapaliya, Ray A. Matsumoto, Arjun Bansal, Xiaobo Lin, Peter T. Cummings, Madhusudan Tyagi, Sheng Dai, Eugene Mamontov

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration (Nat. Energy 2019, 4, 241-248). However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li⁺ions are of similar size in all the solvents, resulting in a universal ∼50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.

Original language	English
Pages (from-to)	2845-2850
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	13
Issue number	12
DOIs	https://doi.org/10.1021/acs.jpclett.2c00487
State	Published - Mar 31 2022

Funding

This work was supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Work at ORNL’s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for U.S. DOE under Contract No. DEAC05-00OR22725. QClimax is a part of the Integrated Computational Environment Modeling and Analysis of Neutron Data (ICE-MAN) (LDRD 8237) project, funded by the Laboratory Directed Research and Development program at ORNL. B.P.T. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract Number DE-AC05-00OR22725.

Funders	Funder number
Scientific User Facilities Division
U.S. Department of Energy	LDRD 8237, DEAC05-00OR22725
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Division of Materials Sciences and Engineering	DE-AC05-00OR22725

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title = "Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent's Mole Fraction",

abstract = "Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration (Nat. Energy 2019, 4, 241-248). However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li+ions are of similar size in all the solvents, resulting in a universal ∼50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.",

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AU - Thapaliya, Bishnu Prasad

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AU - Bansal, Arjun

AU - Lin, Xiaobo

AU - Cummings, Peter T.

AU - Tyagi, Madhusudan

AU - Dai, Sheng

AU - Mamontov, Eugene

PY - 2022/3/31

Y1 - 2022/3/31

N2 - Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration (Nat. Energy 2019, 4, 241-248). However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li+ions are of similar size in all the solvents, resulting in a universal ∼50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.

AB - Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration (Nat. Energy 2019, 4, 241-248). However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li+ions are of similar size in all the solvents, resulting in a universal ∼50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.

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Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent's Mole Fraction

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