TY - JOUR
T1 - Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent's Mole Fraction
AU - Osti, Naresh C.
AU - Thapaliya, Bishnu Prasad
AU - Matsumoto, Ray A.
AU - Bansal, Arjun
AU - Lin, Xiaobo
AU - Cummings, Peter T.
AU - Tyagi, Madhusudan
AU - Dai, Sheng
AU - Mamontov, Eugene
N1 - Funding Information:
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.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
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.
UR - http://www.scopus.com/inward/record.url?scp=85127585364&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.2c00487
DO - 10.1021/acs.jpclett.2c00487
M3 - Article
C2 - 35324215
AN - SCOPUS:85127585364
SN - 1948-7185
VL - 13
SP - 2845
EP - 2850
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 12
ER -