Beyond Simple Dilution: Superior Conductivities from Cosolvation of Acetonitrile/LiTFSI Concentrated Solution with Acetone

Martins, Murillo L.; Sacci, Robert L.; Lin, Xiaobo; Matsumoto, Ray; Popov, Ivan; Cui, Jinlei; Kobayashi, Takeshi; Tyagi, Madhusudan; Guo, Wei; Dai, Sheng; Pruski, Marek; Cummings, Peter T.; Sokolov, Alexei P.; Mamontov, Eugene

doi:10.1021/acs.jpcc.1c09352

Title: Beyond Simple Dilution: Superior Conductivities from Cosolvation of Acetonitrile/LiTFSI Concentrated Solution with Acetone

Journal Article · 26 January 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.1c09352 · OSTI ID:1845802

^[1];

^[1]; Lin, Xiaobo ^[2];

^[2];

^[1]; Cui, Jinlei ^[3];

^[3]; Tyagi, Madhusudan ^[4]; Guo, Wei ^[1];

^[1];

^[3]; Cummings, Peter T. ^[2];

^[5];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Vanderbilt Univ., Nashville, TN (United States)
Iowa State Univ., Ames, IA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Concentrated solutions of Li salts in acetonitrile are promising alternative electrolytes for the next generation of Li batteries as they may exhibit superior electrochemical properties. However, the reduced mobility of the chemical species is a barrier yet to be overcome, and for this, we explore the utilization of acetone as a cosolvent. Although acetone is a polar compound, we find that its addition to the LiTFSI/acetonitrile solution does not follow the trends expected for a simple dilution process. At a low concentration, acetone subtly shifts acetonitrile from the first to extended solvation sheaths of the ions. Still, most of the original structure of the solution is preserved, and mobile high-concentration clusters are formed in the solution. At higher concentrations, the cosolvation promotes cation–anion interactions but with a different nature from those in the original solution and still allows for a further increase in conductivity. Additionally, the non-coordinating fraction of acetonitrile acquires features resembling the pure solvent, which is a possible additional facilitating factor for ionic diffusion.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1845802

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 5 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Beyond Simple Dilution: Superior Conductivities from Cosolvation of Acetonitrile/LiTFSI Concentrated Solution with Acetone

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