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

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

doi:10.1021/acs.jpclett.2c00487

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

Journal Article · Thu Mar 24 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00487· OSTI ID:1860558

^[1]; ^[2]; ^[3]; Bansal, Arjun ^[3]; Lin, Xiaobo ^[3]; Cummings, Peter T. ^[3]; Tyagi, Madhusudan ^[4]; ^[2]; ^[1]

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

We report that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration. 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.

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). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1860558

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 12 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (29)

High‐Voltage Supercapacitors Based on Aqueous Electrolytes Zang, Xining; Shen, Caiwei; Sanghadasa, Mohan ChemElectroChem, Vol. 6, Issue 4 https://doi.org/10.1002/celc.201801225	journal	November 2018
The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies Copley, J. R. D.; Cook, J. C. Chemical Physics, Vol. 292, Issue 2-3 https://doi.org/10.1016/S0301-0104(03)00124-1	journal	August 2003
Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering Osti, N. C.; Coté, A.; Mamontov, E. Chemical Physics, Vol. 465-466 https://doi.org/10.1016/j.chemphys.2015.11.008	journal	February 2016
Simple analytical model for fitting QENS data from liquids Mamontov, E.; Smith, R. W.; Billings, J. J. Physica B: Condensed Matter, Vol. 566 https://doi.org/10.1016/j.physb.2019.01.051	journal	August 2019
Review on supercapacitors: Technologies and materials González, Ander; Goikolea, Eider; Barrena, Jon Andoni Renewable and Sustainable Energy Reviews, Vol. 58 https://doi.org/10.1016/j.rser.2015.12.249	journal	May 2016
Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents Cui, Jinlei; Kobayashi, Takeshi; Sacci, Robert L. The Journal of Physical Chemistry B, Vol. 124, Issue 44 https://doi.org/10.1021/acs.jpcb.0c07582	journal	October 2020
Solvent Dynamics in Solutions of PNIPAM in Water/Methanol Mixtures—A Quasi-Elastic Neutron Scattering Study Kyriakos, Konstantinos; Philipp, Martine; Silvi, Luca The Journal of Physical Chemistry B, Vol. 120, Issue 20 https://doi.org/10.1021/acs.jpcb.6b01200	journal	May 2016
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
Microscopic Dynamics in an Ionic Liquid Augmented with Organic Solvents Osti, Naresh C.; Matsumoto, Ray A.; Thompson, Matthew W. The Journal of Physical Chemistry C, Vol. 123, Issue 32 https://doi.org/10.1021/acs.jpcc.9b05119	journal	July 2019
Solvent Polarity Governs Ion Interactions and Transport in a Solvated Room-Temperature Ionic Liquid Osti, Naresh C.; Van Aken, Katherine L.; Thompson, Matthew W. The Journal of Physical Chemistry Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acs.jpclett.6b02587	journal	December 2016
Water or Anion? Uncovering the Zn ²⁺ Solvation Environment in Mixed Zn(TFSI) ₂ and LiTFSI Water-in-Salt Electrolytes Zhang, Yong; Wan, Gang; Lewis, Nicholas H. C. ACS Energy Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsenergylett.1c01624	journal	September 2021
Pulse-Gradient Spin-Echo ¹ H, ⁷ Li, and ¹⁹ F NMR Diffusion and Ionic Conductivity Measurements of 14 Organic Electrolytes Containing LiN(SO ₂ CF ₃ ) ₂ Hayamizu, Kikuko; Aihara, Yuichi; Arai, Shigemasa The Journal of Physical Chemistry B, Vol. 103, Issue 3 https://doi.org/10.1021/jp9825664	journal	January 1999
Materials for electrochemical capacitors Simon, Patrice; Gogotsi, Yury Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2297	journal	November 2008
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
A review of electrode materials for electrochemical supercapacitors Wang, Guoping; Zhang, Lei; Zhang, Jiujun Chemical Society Reviews, Vol. 41, Issue 2, p. 797-828 https://doi.org/10.1039/C1CS15060J	journal	January 2012
Nanometer-sized dynamic entities in an aqueous system Mamontov, E.; Zolnierczuk, P.; Ohl, M. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP05081A	journal	January 2015
Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions Yu, Zenan; Tetard, Laurene; Zhai, Lei Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03229B	journal	January 2015
A review of electrolyte materials and compositions for electrochemical supercapacitors Zhong, Cheng; Deng, Yida; Hu, Wenbin Chemical Society Reviews, Vol. 44, Issue 21 https://doi.org/10.1039/C5CS00303B	journal	January 2015
Electrolytes for electrochemical energy storage Xia, Lan; Yu, Linpo; Hu, Di Materials Chemistry Frontiers, Vol. 1, Issue 4 https://doi.org/10.1039/C6QM00169F	journal	January 2017
Structure and dynamics of highly concentrated LiTFSI/acetonitrile electrolytes Lundin, Filippa; Aguilera, Luis; Hansen, Henriette Wase Physical Chemistry Chemical Physics, Vol. 23, Issue 25 https://doi.org/10.1039/D1CP02006D	journal	January 2021
Temperature-dependent self-diffusion coefficients of water and six selected molecular liquids for calibration in accurate 1H NMR PFG measurements Holz, Manfred; Heil, Stefan R.; Sacco, Antonio Physical Chemistry Chemical Physics, Vol. 2, Issue 20 https://doi.org/10.1039/b005319h	journal	January 2000
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
Dynamics of liquid acetonitrile at high frequencies Kunz, W.; Calmettes, P.; Bellissent‐Funel, M. ‐C. The Journal of Chemical Physics, Vol. 99, Issue 3 https://doi.org/10.1063/1.465273	journal	August 1993
Quasielastic neutron scattering studies on glass-forming ionic liquids with imidazolium cations Kofu, Maiko; Tyagi, Madhusudan; Inamura, Yasuhiro The Journal of Chemical Physics, Vol. 143, Issue 23 https://doi.org/10.1063/1.4937413	journal	December 2015
Quasielastic neutron scattering study on proton dynamics assisted by water and ammonia molecules confined in MIL-53 Miyatsu, Satoshi; Kofu, Maiko; Shigematsu, Akihito Structural Dynamics, Vol. 8, Issue 5 https://doi.org/10.1063/4.0000122	journal	September 2021
Dynamics of water studied by neutron scattering Teixeira, J.; Bellissent-Funel, M. -C Journal of Physics: Condensed Matter, Vol. 2, Issue S https://doi.org/10.1088/0953-8984/2/S/011	journal	December 1990
Cation Molecular Structure Affects Mobility and Transport of Electrolytes in Porous Carbons Osti, Naresh C.; Dyatkin, Boris; Gallegos, Alejandro Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.0131904jes	journal	January 2019
Fast diffusion in a room temperature ionic liquid confined in mesoporous carbon Chathoth, S. M.; Mamontov, E.; Dai, S. EPL (Europhysics Letters), Vol. 97, Issue 6 https://doi.org/10.1209/0295-5075/97/66004	journal	March 2012
Ionic Liquid-Based Electrolytes for Supercapacitor and Supercapattery Yu, Linpo; Chen, George Z. Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00272	journal	April 2019

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