Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris; Wu, Jianzhong; Gogotsi, Yury; Mamontov, Eugene

doi:10.1021/acs.jpcc.8b02521

Title: Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

Journal Article · Thu Apr 19 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b02521· OSTI ID:1439150

^[1]; Gallegos, Alejandro ^[2];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Drexel Univ., Philadelphia, PA (United States); U.S. Naval Research Lab., Washington, D.C. (United States)
Drexel Univ., Philadelphia, PA (United States)

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF4 volume ratio displaces the larger [TFSI–] anions with smaller [BF4–] ions, leading to an excess adsorption of [Emim+] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. Molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1439150

Alternate ID(s):: OSTI ID: 1482459

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 19; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 44 works

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References (42)

Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
Materials for electrochemical capacitors Simon, Patrice; Gogotsi, Yury Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2297	journal	November 2008
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
Carbon-Based Supercapacitors Produced by Activation of Graphene Zhu, Y.; Murali, S.; Stoller, M. D. Science, Vol. 332, Issue 6037, p. 1537-1541 https://doi.org/10.1126/science.1200770	journal	May 2011
Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems Simon, P.; Gogotsi, Y. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar200306b	journal	June 2012
Carbons and Electrolytes for Advanced Supercapacitors Béguin, François; Presser, Volker; Balducci, Andrea Advanced Materials, Vol. 26, Issue 14, p. 2219-2251 https://doi.org/10.1002/adma.201304137	journal	February 2014
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
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
Energy applications of ionic liquids Wishart, James F. Energy & Environmental Science, Vol. 2, Issue 9 https://doi.org/10.1039/b906273d	journal	January 2009
Temperature stable supercapacitors based on ionic liquid and mixed functionalized carbon nanomaterials Borges, R. S.; Ribeiro, H.; Lavall, R. L. Journal of Solid State Electrochemistry, Vol. 16, Issue 11 https://doi.org/10.1007/s10008-012-1785-5	journal	June 2012
Graphene-Based Supercapacitors Using Eutectic Ionic Liquid Mixture Electrolyte Lin, Zifeng; Taberna, Pierre-Louis; Simon, Patrice Electrochimica Acta, Vol. 206 https://doi.org/10.1016/j.electacta.2015.12.097	journal	July 2016
Controlled Electrochemical Charge Injection to Maximize the Energy Density of Supercapacitors Weng, Zhe; Li, Feng; Wang, Da-Wei Angewandte Chemie International Edition, Vol. 52, Issue 13 https://doi.org/10.1002/anie.201209259	journal	February 2013
Adjustment of electrodes potential window in an asymmetric carbon/MnO2 supercapacitor Demarconnay, L.; Raymundo-Piñero, E.; Béguin, F. Journal of Power Sources, Vol. 196, Issue 1 https://doi.org/10.1016/j.jpowsour.2010.06.013	journal	January 2011
Improving Performance of Electric Double Layer Capacitors with a Mixture of Ionic Liquid and Acetonitrile as the Electrolyte by Using Mass-Balancing Carbon Electrodes Vaquero, Susana; Palma, Jesus; Anderson, Marc Journal of The Electrochemical Society, Vol. 160, Issue 11 https://doi.org/10.1149/2.063311jes	journal	January 2013
A new type of high energy asymmetric capacitor with nanoporous carbon electrodes in aqueous electrolyte Khomenko, V.; Raymundo-Piñero, E.; Béguin, F. Journal of Power Sources, Vol. 195, Issue 13 https://doi.org/10.1016/j.jpowsour.2010.01.006	journal	July 2010
Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury Angewandte Chemie, Vol. 127, Issue 16 https://doi.org/10.1002/ange.201412257	journal	March 2015
Viscosity of Ionic Liquid–Ionic Liquid Mixtures Fillion, Joseph J.; Brennecke, Joan F. Journal of Chemical & Engineering Data, Vol. 62, Issue 6 https://doi.org/10.1021/acs.jced.7b00221	journal	May 2017
Emerging Evidences of Mesoscopic-Scale Complexity in Neat Ionic Liquids and Their Mixtures Russina, Olga; Lo Celso, Fabrizio; Plechkova, Natalia V. The Journal of Physical Chemistry Letters, Vol. 8, Issue 6 https://doi.org/10.1021/acs.jpclett.6b02811	journal	February 2017
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
Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures Lian, C.; Liu, K.; Van Aken, K. L. ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00010	journal	April 2016
The Electric Double Layer Has a Life of Its Own Merlet, Céline; Limmer, David T.; Salanne, Mathieu The Journal of Physical Chemistry C, Vol. 118, Issue 32 https://doi.org/10.1021/jp503224w	journal	June 2014
Electrolyte surface tension in the modified Poisson-Boltzmann approximation Bhuiyan, L. B.; Bratko, D.; Outhwaite, C. W. The Journal of Physical Chemistry, Vol. 95, Issue 1 https://doi.org/10.1021/j100154a061	journal	January 1991
Density Functional Study of the Electric Double Layer Formed by a High Density Electrolyte Henderson, Douglas; Lamperski, Stanisław; Jin, Zhehui The Journal of Physical Chemistry B, Vol. 115, Issue 44 https://doi.org/10.1021/jp2078105	journal	November 2011
A classical density functional theory for interfacial layering of ionic liquids Wu, Jianzhong; Jiang, Tao; Jiang, De-en Soft Matter, Vol. 7, Issue 23 https://doi.org/10.1039/c1sm06089a	journal	January 2011
MnO2/onion-like carbon nanocomposites for pseudocapacitors Wang, Ye; Yu, Siu Fung; Sun, Cheng Yue Journal of Materials Chemistry, Vol. 22, Issue 34 https://doi.org/10.1039/c2jm33558a	journal	January 2012
Outstanding performance of activated graphene based supercapacitors in ionic liquid electrolyte from −50 to 80°C Tsai, Wan-Yu; Lin, Rongying; Murali, Shanthi Nano Energy, Vol. 2, Issue 3 https://doi.org/10.1016/j.nanoen.2012.11.006	journal	May 2013
On-chip micro-supercapacitors for operation in a wide temperature range Huang, Peihua; Pech, David; Lin, Rongying Electrochemistry Communications, Vol. 36 https://doi.org/10.1016/j.elecom.2013.09.003	journal	November 2013
Influence of the structure of carbon onions on their electrochemical performance in supercapacitor electrodes McDonough, John K.; Frolov, Andrey I.; Presser, Volker Carbon, Vol. 50, Issue 9 https://doi.org/10.1016/j.carbon.2011.12.022	journal	August 2012
Graphitization as a Universal Tool to Tailor the Potential-Dependent Capacitance of Carbon Supercapacitors Weingarth, Daniel; Zeiger, Marco; Jäckel, Nicolas Advanced Energy Materials, Vol. 4, Issue 13 https://doi.org/10.1002/aenm.201400316	journal	May 2014
Effect of nanostructured carbon support on copper electrocatalytic activity toward CO2 electroreduction to hydrocarbon fuels Baturina, Olga; Lu, Qin; Xu, Feng Catalysis Today, Vol. 288 https://doi.org/10.1016/j.cattod.2016.11.001	journal	June 2017
Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu Carbon, Vol. 129 https://doi.org/10.1016/j.carbon.2017.12.001	journal	April 2018
Influence of Surface Oxidation on Ion Dynamics and Capacitance in Porous and Nonporous Carbon Electrodes Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene The Journal of Physical Chemistry C, Vol. 120, Issue 16 https://doi.org/10.1021/acs.jpcc.6b01204	journal	April 2016
Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M. Progress in Natural Science: Materials International, Vol. 25, Issue 6 https://doi.org/10.1016/j.pnsc.2015.11.007	journal	December 2015
Mixtures of ionic liquids Niedermeyer, Heiko; Hallett, Jason P.; Villar-Garcia, Ignacio J. Chemical Society Reviews, Vol. 41, Issue 23 https://doi.org/10.1039/c2cs35177c	journal	January 2012
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
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
Effect of Metal Ion Intercalation on the Structure of MXene and Water Dynamics on its Internal Surfaces Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza ACS Applied Materials & Interfaces, Vol. 8, Issue 14 https://doi.org/10.1021/acsami.6b01490	journal	March 2016
Translational and Reorientational Dynamics of an Imidazolium-Based Ionic Liquid Aoun, Bachir; González, Miguel A.; Ollivier, Jacques The Journal of Physical Chemistry Letters, Vol. 1, Issue 17 https://doi.org/10.1021/jz100856t	journal	August 2010
Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential Mahurin, Shannon M.; Mamontov, Eugene; Thompson, Matthew W. Applied Physics Letters, Vol. 109, Issue 14 https://doi.org/10.1063/1.4964130	journal	October 2016
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
An unusual slowdown of fast diffusion in a room temperature ionic liquid confined in mesoporous carbon Chathoth, S. M.; Mamontov, E.; Fulvio, P. F. EPL (Europhysics Letters), Vol. 102, Issue 1 https://doi.org/10.1209/0295-5075/102/16004	journal	April 2013
Ion Dynamics in Porous Carbon Electrodes in Supercapacitors Using in Situ Infrared Spectroelectrochemistry Richey, Francis W.; Dyatkin, Boris; Gogotsi, Yury Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja406120e	journal	August 2013

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Status review on the MEMS-based flexible supercapacitors Patil, Swati; Lee, Dong-Weon Journal of Micromechanics and Microengineering, Vol. 29, Issue 9 https://doi.org/10.1088/1361-6439/ab1c9b	journal	June 2019
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