Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Cui, Jinlei; Kobayashi, Takeshi; Sacci, Robert L.; Matsumoto, Ray A.; Cummings, Peter T.; Pruski, Marek

doi:10.1021/acs.jpcb.0c07582

Title: Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Abstract

Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM+][TFSI–]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340-1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ~1 solvent molecule. Themore »« less

Authors:

Cui, Jinlei ^[1];

^[1];

^[2];

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

^[4]

Ames Lab., Ames, IA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Vanderbilt Univ., Nashville, TN (United States)
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)

Publication Date:: Wed Oct 21 00:00:00 EDT 2020

Research Org.:: Ames Lab., Ames, IA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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

OSTI Identifier:: 1709122

Alternate Identifier(s):: OSTI ID: 1810005; OSTI ID: 1817626

Report Number(s):: IS-J-10,334; IS-J 10,569
Journal ID: ISSN 1520-6106

Grant/Contract Number:: AC02-07CH11358; AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 124; Journal Issue: 44; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transport properties; salts; diffusion; ions; solvents

Citation Formats


                    Cui, Jinlei, Kobayashi, Takeshi, Sacci, Robert L., Matsumoto, Ray A., Cummings, Peter T., and Pruski, Marek. Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcb.0c07582.

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                    Cui, Jinlei, Kobayashi, Takeshi, Sacci, Robert L., Matsumoto, Ray A., Cummings, Peter T., & Pruski, Marek. Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents.  United States.  https://doi.org/10.1021/acs.jpcb.0c07582

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                    Cui, Jinlei, Kobayashi, Takeshi, Sacci, Robert L., Matsumoto, Ray A., Cummings, Peter T., and Pruski, Marek. Wed .  
"Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents".  United States.  https://doi.org/10.1021/acs.jpcb.0c07582.  https://www.osti.gov/servlets/purl/1709122.

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@article{osti_1709122,

  title        = {Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents},

  author       = {Cui, Jinlei and Kobayashi, Takeshi and Sacci, Robert L. and Matsumoto, Ray A. and Cummings, Peter T. and Pruski, Marek},

  abstractNote = {Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM+][TFSI–]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340-1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ~1 solvent molecule. The scarcity of solvent–ion interactions explains the fact that the diffusivity of ions in the mixture significantly depends on the viscosity of the solvent.},

  doi          = {10.1021/acs.jpcb.0c07582},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 44,

  volume       = 124,

  place        = {United States},

  year         = {Wed Oct 21 00:00:00 EDT 2020},

  month        = {Wed Oct 21 00:00:00 EDT 2020}

}

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Title: Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Abstract

Citation Formats

Quantitative modeling of factors determining Ragone plots for batteries and electrochemical capacitors journal, December 1996

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Review on supercapacitors: Technologies and materials journal, May 2016

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Analysis of the dynamic behavior changes of supercapacitors during calendar life test under several voltages and temperatures conditions journal, September 2009

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Carbon Materials for Chemical Capacitive Energy Storage journal, September 2011

Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems journal, June 2012

Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors journal, January 1997

Novel insight into neutral medium as electrolyte for high-voltage supercapacitors journal, January 2012

Exploring the large voltage range of carbon/carbon supercapacitors in aqueous lithium sulfate electrolyte journal, January 2012

Effect of accelerated ageing on the performance of high voltage carbon/carbon electrochemical capacitors in salt aqueous electrolyte journal, June 2014

Electrolyte selection for supercapacitive devices: a critical review journal, January 2019

The effect of ILs as co-salts in electrolytes for high voltage supercapacitors journal, February 2019

Ionic Liquids for Clean Technology journal, April 1997

CHEMISTRY: Ionic Liquids--Solvents of the Future? journal, October 2003

Electrochemical Properties of Imidazolium Salt Electrolytes for Electrochemical Capacitor Applications journal, January 1999

Electrochemical properties of novel ionic liquids for electric double layer capacitor applications journal, September 2004

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors journal, March 2015

Ionic liquid–solvent mixtures as supercapacitor electrolytes for extreme temperature operation journal, January 2012

Ionic-liquid materials for the electrochemical challenges of the future journal, July 2009

Capacitive Energy Storage from −50 to 100 °C Using an Ionic Liquid Electrolyte journal, September 2011

Ionic Liquids: evidence of the viscosity scale-dependence journal, May 2017

Performance of carbon–carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes journal, September 2010

Structure and dynamics of electrical double layers in organic electrolytes journal, January 2010

New Coarse-Grained Models of Imidazolium Ionic Liquids for Bulk and Interfacial Molecular Simulations journal, March 2012

Effect of ion structure on conductivity in lithium-doped ionic liquid electrolytes: A molecular dynamics study journal, September 2013

Physicochemical Properties of Three Ionic Liquids Containing a Tetracyanoborate Anion and Their Lithium Salt Mixtures journal, July 2014

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes journal, June 2014

Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential journal, October 2016

Solvent Polarity Governs Ion Interactions and Transport in a Solvated Room-Temperature Ionic Liquid journal, December 2016

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces journal, April 2018

Scalable Screening of Soft Matter: A Case Study of Mixtures of Ionic Liquids and Organic Solvents journal, January 2019

Ion Pairing Controls Physical Properties of Ionic Liquid-Solvent Mixtures journal, October 2019

AC-impedance spectroscopy of anodic reactions with adsorbed intermediates: electro-oxidations of 2-propanol and methanol on carbon-supported Pt catalyst journal, November 2004

Dynamic electrochemical impedance spectroscopy, for electrocatalytic reactions journal, June 2014

The influence of a hierarchical porous carbon network on the coherent dynamics of a nanoconfined room temperature ionic liquid: A neutron spin echo and atomistic simulation investigation journal, November 2014

Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering journal, February 2016

Influence of humidity on performance and microscopic dynamics of an ionic liquid in supercapacitor journal, August 2017

Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient journal, January 1965

NMR Studies on Poly(ethylene oxide)-based Polymer Electrolytes with Different Cross-Linking Doped with LiN(SO 2 CF 3 ) 2 . Restricted Diffusion of the Polymer and Lithium Ion and Time-Dependent Diffusion of the Anion journal, April 2003

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 journal, January 1999

Critical Role of Anion–Solvent Interactions for Dynamics of Solvent-in-Salt Solutions journal, March 2020

Ionic mobility in ternary polymer electrolytes for lithium-ion batteries journal, December 2012

Li + -Ion Dynamics in β-Li 3 PS 4 Observed by NMR: Local Hopping and Long-Range Transport journal, June 2018

Diffusion, conductivity and DSC studies of a polymer gel electrolyte composed of cross-linked PEO, Î³-butyrolactone and LiBF4 journal, March 1998

Direct Observation of N 2 Self-Diffusion in Zeolitic Adsorbents Using 15 N PFG NMR journal, January 1996

Gas diffusion in zeolite beds: PFG NMR evidence for different tortuosity factors in the Knudsen and bulk regimes journal, November 2003

Gas Diffusion in Polycrystalline Silicalite Membranes Investigated by 1 H Pulse Field-Gradient NMR journal, July 2005

PFG NMR diffusion measurements of CH4 and CO2 through large ZSM-58-crystals journal, December 2013

A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples journal, April 2004

Suppression of Convection Artifacts in Stimulated-Echo Diffusion Experiments. Double-Stimulated-Echo Experiments journal, April 1997

Convection Compensation in Gradient Enhanced Nuclear Magnetic Resonance Spectroscopy journal, May 1998

LXXV. A dynamical theory of diffusion for non-electrolytes and the molecular mass of albumin journal, June 1905

Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation journal, April 2005

Temperature-dependence of self-diffusion for benzene and carbon tetrachloride journal, January 1970

Quantitative modeling of factors determining Ragone plots for batteries and electrochemical capacitors
journal, December 1996

What Are Batteries, Fuel Cells, and Supercapacitors?
journal, October 2004

Review on supercapacitors: Technologies and materials
journal, May 2016

Theory of Ragone plots
journal, December 2000

Principles and applications of electrochemical capacitors
journal, May 2000

Analysis of the dynamic behavior changes of supercapacitors during calendar life test under several voltages and temperatures conditions
journal, September 2009

R&D considerations for the performance and application of electrochemical capacitors
journal, December 2007

Electrochemical performance of carbon onions, nanodiamonds, carbon black and multiwalled nanotubes in electrical double layer capacitors
journal, November 2007

Graphene-Based Ultracapacitors
journal, October 2008

Carbon nanotubes and their composites in electrochemical applications
journal, January 2011

Carbon Materials for Chemical Capacitive Energy Storage
journal, September 2011

Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems
journal, June 2012

Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors
journal, January 1997

Novel insight into neutral medium as electrolyte for high-voltage supercapacitors
journal, January 2012

Exploring the large voltage range of carbon/carbon supercapacitors in aqueous lithium sulfate electrolyte
journal, January 2012

Effect of accelerated ageing on the performance of high voltage carbon/carbon electrochemical capacitors in salt aqueous electrolyte
journal, June 2014

Electrolyte selection for supercapacitive devices: a critical review
journal, January 2019

The effect of ILs as co-salts in electrolytes for high voltage supercapacitors
journal, February 2019

Ionic Liquids for Clean Technology
journal, April 1997

CHEMISTRY: Ionic Liquids--Solvents of the Future?
journal, October 2003

Electrochemical Properties of Imidazolium Salt Electrolytes for Electrochemical Capacitor Applications
journal, January 1999

Electrochemical properties of novel ionic liquids for electric double layer capacitor applications
journal, September 2004

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors
journal, March 2015

Ionic liquid–solvent mixtures as supercapacitor electrolytes for extreme temperature operation
journal, January 2012

Ionic-liquid materials for the electrochemical challenges of the future
journal, July 2009

Capacitive Energy Storage from −50 to 100 °C Using an Ionic Liquid Electrolyte
journal, September 2011

Ionic Liquids: evidence of the viscosity scale-dependence
journal, May 2017

Performance of carbon–carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes
journal, September 2010

Structure and dynamics of electrical double layers in organic electrolytes
journal, January 2010

New Coarse-Grained Models of Imidazolium Ionic Liquids for Bulk and Interfacial Molecular Simulations
journal, March 2012

Effect of ion structure on conductivity in lithium-doped ionic liquid electrolytes: A molecular dynamics study
journal, September 2013

Physicochemical Properties of Three Ionic Liquids Containing a Tetracyanoborate Anion and Their Lithium Salt Mixtures
journal, July 2014

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes
journal, June 2014

Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential
journal, October 2016

Solvent Polarity Governs Ion Interactions and Transport in a Solvated Room-Temperature Ionic Liquid
journal, December 2016

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces
journal, April 2018

Scalable Screening of Soft Matter: A Case Study of Mixtures of Ionic Liquids and Organic Solvents
journal, January 2019

Ion Pairing Controls Physical Properties of Ionic Liquid-Solvent Mixtures
journal, October 2019

AC-impedance spectroscopy of anodic reactions with adsorbed intermediates: electro-oxidations of 2-propanol and methanol on carbon-supported Pt catalyst
journal, November 2004

Dynamic electrochemical impedance spectroscopy, for electrocatalytic reactions
journal, June 2014

The influence of a hierarchical porous carbon network on the coherent dynamics of a nanoconfined room temperature ionic liquid: A neutron spin echo and atomistic simulation investigation
journal, November 2014

Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering
journal, February 2016

Influence of humidity on performance and microscopic dynamics of an ionic liquid in supercapacitor
journal, August 2017

Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient
journal, January 1965

NMR Studies on Poly(ethylene oxide)-based Polymer Electrolytes with Different Cross-Linking Doped with LiN(SO ₂ CF ₃ ) ₂ . Restricted Diffusion of the Polymer and Lithium Ion and Time-Dependent Diffusion of the Anion
journal, April 2003

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
journal, January 1999

Critical Role of Anion–Solvent Interactions for Dynamics of Solvent-in-Salt Solutions
journal, March 2020

Ionic mobility in ternary polymer electrolytes for lithium-ion batteries
journal, December 2012

Li ⁺ -Ion Dynamics in β-Li ₃ PS ₄ Observed by NMR: Local Hopping and Long-Range Transport
journal, June 2018

Diffusion, conductivity and DSC studies of a polymer gel electrolyte composed of cross-linked PEO, Î³-butyrolactone and LiBF4
journal, March 1998

Direct Observation of N ₂ Self-Diffusion in Zeolitic Adsorbents Using ¹⁵ N PFG NMR
journal, January 1996

Gas diffusion in zeolite beds: PFG NMR evidence for different tortuosity factors in the Knudsen and bulk regimes
journal, November 2003

Gas Diffusion in Polycrystalline Silicalite Membranes Investigated by ¹ H Pulse Field-Gradient NMR
journal, July 2005

PFG NMR diffusion measurements of CH4 and CO2 through large ZSM-58-crystals
journal, December 2013

A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples
journal, April 2004

Suppression of Convection Artifacts in Stimulated-Echo Diffusion Experiments. Double-Stimulated-Echo Experiments
journal, April 1997

Convection Compensation in Gradient Enhanced Nuclear Magnetic Resonance Spectroscopy
journal, May 1998

LXXV. A dynamical theory of diffusion for non-electrolytes and the molecular mass of albumin
journal, June 1905

Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation
journal, April 2005

Temperature-dependence of self-diffusion for benzene and carbon tetrachloride
journal, January 1970