Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion

Penley, Drace; Wang, Xiaoyu; Lee, Yun-Yang; Garaga, Mounesha N.; Ghahremani, Raziyeh; Greenbaum, Steve; Maginn, Edward J.; Gurkan, Burcu

doi:10.1021/acs.jced.2c00294

Title: Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion

Journal Article · Tue Jul 19 00:00:00 EDT 2022 · Journal of Chemical and Engineering Data

DOI:https://doi.org/10.1021/acs.jced.2c00294· OSTI ID:1882218

Penley, Drace ^[1];

^[2];

^[1]; Garaga, Mounesha N. ^[3]; Ghahremani, Raziyeh ^[1];

^[3];

^[2];

^[1]

Case Western Reserve Univ., Cleveland, OH (United States)
Univ. of Notre Dame, IN (United States)
Hunter College, New York, NY (United States)

The solvation structure and transport properties of Li⁺ in ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium cyano(trifluoromethanesulfonyl)imide [PYR₁₄][CTFSI] and [Li][CTFSI] (0 ≤ x_Li ≤ 0.7) were studied by Raman and Nuclear Magnetic Resonance (NMR) diffusometry, and molecular dynamics (MD) simulations. At x_Li < 0.3, Li⁺ coordination is dominated by the cyano group. As x_Li is increased, free cyano-sites become limited, resulting in increased coordination via the sulfonyl group. Here, the 1:1 mixture of the symmetric anions bis(trifluoromethanesulfonyl)imide ([TFSI]) and dicyanamide ([DCA]) results in similar physical properties as the IL with [CTFSI]. However, anion asymmetry is shown to increase Li-salt solubility and promote Li+ transference. The lifetimes of Li⁺-cyano coordination for [CTFSI] are calculated to be shorter than those for [DCA], indicating that the competition from the sulfonyl group weakens its solvation with Li⁺. This resulted in higher Li⁺ transference for the electrolyte with [CTFSI]. In relation to the utility of these electrolytes in energy storage, the Li–LiFePO₄ half cells assembled with IL electrolyte (x_Li = 0.3, 0.5, and 0.7) demonstrated a nominal capacity of 140 mAh/g at 0.1C rate and 90 °C where the cell with x_Li = 0.7 IL electrolyte demonstrated 61% capacity retention after 100 cycles and superior rate capability owing to increased electrochemical stability.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

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

Grant/Contract Number:: SC0019409

OSTI ID:: 1882218

Journal Information:: Journal of Chemical and Engineering Data, Vol. 67, Issue 8; ISSN 0021-9568

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

On the application of ionic liquids for rechargeable Li batteries: High voltage systems Borgel, V.; Markevich, E.; Aurbach, D. Journal of Power Sources, Vol. 189, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.08.099	journal	April 2009
Ionic-liquid materials for the electrochemical challenges of the future Armand, Michel; Endres, Frank; MacFarlane, Douglas R. Nature Materials, Vol. 8, Issue 8, p. 621-629 https://doi.org/10.1038/nmat2448	journal	July 2009
Different roles of ionic liquids in lithium batteries Eftekhari, Ali; Liu, Yang; Chen, Pu Journal of Power Sources, Vol. 334 https://doi.org/10.1016/j.jpowsour.2016.10.025	journal	December 2016
Ionic liquids as safe electrolyte components for Li-metal and Li-ion batteries Navarra, Maria Assunta MRS Bulletin, Vol. 38, Issue 7 https://doi.org/10.1557/mrs.2013.152	journal	July 2013
Effect of ionic liquid as a flame-retarding additive on the cycling performance and thermal stability of lithium-ion batteries Bae, Seo-Youn; Shim, Eun-Gi; Kim, Dong-Won Journal of Power Sources, Vol. 244 https://doi.org/10.1016/j.jpowsour.2013.01.100	journal	December 2013
Ionic liquids as electrolytes Galiński, Maciej; Lewandowski, Andrzej; Stępniak, Izabela Electrochimica Acta, Vol. 51, Issue 26 https://doi.org/10.1016/j.electacta.2006.03.016	journal	August 2006
Structure and Transport Properties of Lithium-Doped Aprotic and Protic Ionic Liquid Electrolytes: Insights from Molecular Dynamics Simulations Nasrabadi, Amir Taghavi; Ganesan, Venkat The Journal of Physical Chemistry B, Vol. 123, Issue 26 https://doi.org/10.1021/acs.jpcb.9b04477	journal	June 2019
Structure and lifetimes in ionic liquids and their mixtures Gehrke, Sascha; von Domaros, Michael; Clark, Ryan Faraday Discussions, Vol. 206 https://doi.org/10.1039/C7FD00166E	journal	January 2018
Computational and Experimental Investigation of Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF ₄ ] Haskins, Justin B.; Bennett, William R.; Wu, James J. The Journal of Physical Chemistry B, Vol. 118, Issue 38 https://doi.org/10.1021/jp5061705	journal	September 2014
Concentrated Ionic‐Liquid‐Based Electrolytes for High‐Voltage Lithium Batteries with Improved Performance at Room Temperature Gao, Xinpei; Wu, Fanglin; Mariani, Alessandro ChemSusChem, Vol. 12, Issue 18 https://doi.org/10.1002/cssc.201901739	journal	August 2019
Improved Stability and Rate Capability of Ionic Liquid Electrolyte with High Concentration of LiFSI Heist, Ashley; Lee, Se-Hee Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0381910jes	journal	January 2019
Novel Na ⁺ Ion Diffusion Mechanism in Mixed Organic–Inorganic Ionic Liquid Electrolyte Leading to High Na ⁺ Transference Number and Stable, High Rate Electrochemical Cycling of Sodium Cells. Forsyth, Maria; Yoon, Hyungook; Chen, Fangfang The Journal of Physical Chemistry C, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcc.5b11746	journal	February 2016
Ionic liquid based lithium battery electrolytes: fundamental benefits of utilising both TFSI and FSI anions? Kerner, M.; Plylahan, N.; Scheers, J. Physical Chemistry Chemical Physics, Vol. 17, Issue 29 https://doi.org/10.1039/C5CP01891A	journal	January 2015
Computational Investigation of Mixed Anion Effect on Lithium Coordination and Transport in Salt Concentrated Ionic Liquid Electrolytes Chen, Fangfang; Forsyth, Maria The Journal of Physical Chemistry Letters, Vol. 10, Issue 23 https://doi.org/10.1021/acs.jpclett.9b02416	journal	November 2019
Pyrrolidinium Ionic Liquid Electrolyte with Bis(trifluoromethylsulfonyl)imide and Bis(fluorosulfonyl)imide Anions: Lithium Solvation and Mobility, and Performance in Lithium Metal–Lithium Iron Phosphate Batteries Huang, Qianwen; Lee, Yun-Yang; Gurkan, Burcu Industrial & Engineering Chemistry Research, Vol. 58, Issue 50 https://doi.org/10.1021/acs.iecr.9b03202	journal	October 2019
Solvation Structure and Dynamics of Li ⁺ in Ternary Ionic Liquid–Lithium Salt Electrolytes Huang, Qianwen; Lourenço, Tuanan C.; Costa, Luciano T. The Journal of Physical Chemistry B, Vol. 123, Issue 2 https://doi.org/10.1021/acs.jpcb.8b08859	journal	December 2018
Effect of mixed anions on the transport properties and performance of an ionic liquid-based electrolyte for lithium-ion batteries Chaudoy, Victor; Jacquemin, Johan; Tran-Van, François Pure and Applied Chemistry, Vol. 91, Issue 8 https://doi.org/10.1515/pac-2018-1006	journal	July 2019
Transport Properties and Phase Behaviour in Binary and Ternary Ionic Liquid Electrolyte Systems of Interest in Lithium Batteries Bayley, Paul M.; Best, Adam S.; MacFarlane, Douglas R. ChemPhysChem, Vol. 12, Issue 4 https://doi.org/10.1002/cphc.201000909	journal	January 2011
The influence of cations on lithium ion coordination and transport in ionic liquid electrolytes: a MD simulation study Lesch, Volker; Li, Zhe; Bedrov, Dmitry Physical Chemistry Chemical Physics, Vol. 18, Issue 1 https://doi.org/10.1039/C5CP05111H	journal	January 2016
Relevance of ion clusters for Li transport at elevated salt concentrations in [Pyr _12O1 ][FTFSI] ionic liquid-based electrolytes Brinkkötter, Marc; Giffin, Guinevere A.; Moretti, Arianna Chemical Communications, Vol. 54, Issue 34 https://doi.org/10.1039/C8CC01416G	journal	January 2018
Connection between Lithium Coordination and Lithium Diffusion in [Pyr _12O1 ][FTFSI] Ionic Liquid Electrolytes Giffin, Guinevere A.; Moretti, Arianna; Jeong, Sangsik ChemSusChem, Vol. 11, Issue 12 https://doi.org/10.1002/cssc.201702288	journal	February 2018
Li Coordination of a Novel Asymmetric Anion in Ionic Liquid-in-Li Salt Electrolytes Nürnberg, Pinchas; Lozinskaya, Elena I.; Shaplov, Alexander S. The Journal of Physical Chemistry B, Vol. 124, Issue 5 https://doi.org/10.1021/acs.jpcb.9b11051	journal	January 2020
Decoupling effective Li+ ion conductivity from electrolyte viscosity for improved room-temperature cell performance Giffin, Guinevere A.; Moretti, Arianna; Jeong, Sangsik Journal of Power Sources, Vol. 342 https://doi.org/10.1016/j.jpowsour.2016.12.071	journal	February 2017
Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes Yoon, Hyungook; Best, Adam S.; Forsyth, Maria Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP05333H	journal	January 2015
Phase Behavior of Ionic Liquid−LiX Mixtures: Pyrrolidinium Cations and TFSI ^- Anions Henderson, Wesley A.; Passerini, Stefano Chemistry of Materials, Vol. 16, Issue 15 https://doi.org/10.1021/cm049942j	journal	July 2004
Investigation of the N -butyl- N -methyl pyrrolidinium trifluoromethanesulfonyl- N -cyanoamide (PYR 14 TFSAM) ionic liquid as electrolyte for Li-ion battery Hoffknecht, Jan-Philipp; Drews, Mathias; He, Xin Electrochimica Acta, Vol. 250 https://doi.org/10.1016/j.electacta.2017.08.020	journal	October 2017
Conductivity and transference number measurements on polymer electrolytes Bruce, P. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90304-9	journal	September 1988
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient Stejskal, E. O.; Tanner, J. E. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695690	journal	January 1965
Assessing the Ion Transport Properties of Highly Concentrated Non‐Flammable Electrolytes in a Commercial Li‐Ion Battery Cell Sälzer, Fabian; Pateras Pescara, Lars; Franke, Felix Batteries & Supercaps, Vol. 3, Issue 1 https://doi.org/10.1002/batt.201900111	journal	October 2019
Cross-linked polymeric ionic liquids ion gel electrolytes by in situ radical polymerization Chen, Liya; Fu, Jifang; Lu, Qi Chemical Engineering Journal, Vol. 378 https://doi.org/10.1016/j.cej.2019.122245	journal	December 2019
Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes Pesko, Danielle M.; Timachova, Ksenia; Bhattacharya, Rajashree Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0581711jes	journal	January 2017
Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions Balsara, Nitash P.; Newman, John Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0651514jes	journal	January 2015
Lithium solvation and diffusion in the 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid Duluard, Sandrine; Grondin, Joseph; Bruneel, Jean-Luc Journal of Raman Spectroscopy, Vol. 39, Issue 5 https://doi.org/10.1002/jrs.1896	journal	January 2008
Electrochemical and NMR characterizations of mixed polymer electrolytes based on oligoether sulfate and imide salts Chauvin, C.; Alloin, F.; Judeinstein, P. Electrochimica Acta, Vol. 52, Issue 3 https://doi.org/10.1016/j.electacta.2006.07.023	journal	November 2006
Analysis of Recent Measurements of the Viscosity of Glasses Fulcher, Gordon S. Journal of the American Ceramic Society, Vol. 8, Issue 6 https://doi.org/10.1111/j.1151-2916.1925.tb16731.x	journal	June 1925
Spectroscopic Identification of the Lithium Ion Transporting Species in LiTFSI-Doped Ionic Liquids Lassègues, Jean-Claude; Grondin, Joseph; Aupetit, Christian The Journal of Physical Chemistry A, Vol. 113, Issue 1 https://doi.org/10.1021/jp806124w	journal	January 2009
Development and testing of a general amber force field Wang, Junmei; Wolf, Romain M.; Caldwell, James W. Journal of Computational Chemistry, Vol. 25, Issue 9 https://doi.org/10.1002/jcc.20035	journal	January 2004
A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model Bayly, Christopher I.; Cieplak, Piotr; Cornell, Wendy The Journal of Physical Chemistry, Vol. 97, Issue 40 https://doi.org/10.1021/j100142a004	journal	October 1993
Automatic atom type and bond type perception in molecular mechanical calculations Wang, Junmei; Wang, Wei; Kollman, Peter A. Journal of Molecular Graphics and Modelling, Vol. 25, Issue 2 https://doi.org/10.1016/j.jmgm.2005.12.005	journal	October 2006
Charge Scaling Manifesto: A Way of Reconciling the Inherently Macroscopic and Microscopic Natures of Molecular Simulations Kirby, Brian J.; Jungwirth, Pavel The Journal of Physical Chemistry Letters, Vol. 10, Issue 23 https://doi.org/10.1021/acs.jpclett.9b02652	journal	November 2019
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
TRAVIS—A free analyzer for trajectories from molecular simulation Brehm, M.; Thomas, M.; Gehrke, S. The Journal of Chemical Physics, Vol. 152, Issue 16 https://doi.org/10.1063/5.0005078	journal	April 2020
TRAVIS - A Free Analyzer and Visualizer for Monte Carlo and Molecular Dynamics Trajectories Brehm, Martin; Kirchner, Barbara Journal of Chemical Information and Modeling, Vol. 51, Issue 8 https://doi.org/10.1021/ci200217w	journal	July 2011
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method Zhang, Yong; Otani, Akihito; Maginn, Edward J. Journal of Chemical Theory and Computation, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jctc.5b00351	journal	July 2015
Pulsed-Gradient Spin−Echo ¹ H and ¹⁹ F NMR Ionic Diffusion Coefficient, Viscosity, and Ionic Conductivity of Non-Chloroaluminate Room-Temperature Ionic Liquids Noda, Akihiro; Hayamizu, Kikuko; Watanabe, Masayoshi The Journal of Physical Chemistry B, Vol. 105, Issue 20 https://doi.org/10.1021/jp004132q	journal	May 2001
Estimates of Electrical Conductivity from Molecular Dynamics Simulations: How to Invest the Computational Effort Kubisiak, Piotr; Eilmes, Andrzej The Journal of Physical Chemistry B, Vol. 124, Issue 43 https://doi.org/10.1021/acs.jpcb.0c07704	journal	October 2020
MD Simulations of the Formation of Stable Clusters in Mixtures of Alkaline Salts and Imidazolium-Based Ionic Liquids Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia The Journal of Physical Chemistry B, Vol. 117, Issue 11 https://doi.org/10.1021/jp312669r	journal	March 2013
A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T. The Journal of Chemical Physics, Vol. 148, Issue 19 https://doi.org/10.1063/1.5016276	journal	May 2018
Energetics of Li+ Coordination with Asymmetric Anions in Ionic Liquids by Density Functional Theory Penley, Drace; Vicchio, Stephen P.; Getman, Rachel B. Frontiers in Energy Research, Vol. 9 https://doi.org/10.3389/fenrg.2021.725010	journal	October 2021

Similar Records

Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

Journal Article · Tue Mar 06 00:00:00 EST 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1882218

Das, Laboni; Kumar, Rahul; Maity, Dilip K.; +3 more

Study of Ether-, Alcohol-, or Cyano-Functionalized Ionic Liquids Using Inverse Gas Chromatography

Journal Article · Fri Jan 01 00:00:00 EST 2010 · Journal of Chemical & Engineering Data · OSTI ID:1882218

Revelli, Anne-Laure; Mutelet, Fabrice; Jaubert, Jean-Noel; +4 more

From Salt in Solution to Solely Ions: Solvation of Methyl Viologen in Deep Eutectic Solvents and Ionic Liquids

Journal Article · Fri Jun 26 00:00:00 EDT 2020 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1882218

Klein, Jeffrey M.; Squire, Henry; Dean, William; +1 more

Related Subjects

25 ENERGY STORAGE
Anions
Diffusion
Electrolytes
Solvation
Viscosity

Title: Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion

Citation Formats

References (50)

Similar Records

Related Subjects