Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Gainaru, Catalin P.; Stacy, Eric W.; Bocharova, Vera; Gobet, Mallory; Holt, Adam P.; Saito, Tomonori; Greenbaum, Steve; Sokolov, Alexei P.

doi:10.1021/acs.jpcb.6b08567

Title: Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Abstract

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.

Authors:

Gainaru, Catalin P. ^[1]; Technische Univ. Dortmund, Dortmund ^[2]; Stacy, Eric W. ^[1]; Bocharova, Vera ^[3]; Gobet, Mallory ^[4]; Holt, Adam P. ^[1]; Saito, Tomonori ^[3]; Greenbaum, Steve ^[4]; Sokolov, Alexei P. ^[1]; Oak Ridge National Lab. ^[5]

Univ. of Tennessee, Knoxville, TN (United States)
(Germany)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Hunter College of the City University of New York, New York, NY (United States)
(ORNL), Oak Ridge, TN (United States)

Publication Date:: Wed Sep 28 00:00:00 EDT 2016

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

Sponsoring Org.:: USDOE Laboratory Directed Research and Development (LDRD) Program

OSTI Identifier:: 1337501

Grant/Contract Number:: 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: 120; Journal Issue: 42; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats


                    Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., and Oak Ridge National Lab. Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.jpcb.6b08567.

Copy to clipboard


                    Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., & Oak Ridge National Lab. Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity.  United States.  https://doi.org/10.1021/acs.jpcb.6b08567

Copy to clipboard


                    Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., and Oak Ridge National Lab. Wed .  
"Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity".  United States.  https://doi.org/10.1021/acs.jpcb.6b08567.  https://www.osti.gov/servlets/purl/1337501.

Copy to clipboard


                    
@article{osti_1337501,

  title        = {Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity},

  author       = {Gainaru, Catalin P. and Technische Univ. Dortmund, Dortmund and Stacy, Eric W. and Bocharova, Vera and Gobet, Mallory and Holt, Adam P. and Saito, Tomonori and Greenbaum, Steve and Sokolov, Alexei P. and Oak Ridge National Lab.},

  abstractNote = {Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.},

  doi          = {10.1021/acs.jpcb.6b08567},

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

  number       = 42,

  volume       = 120,

  place        = {United States},

  year         = {Wed Sep 28 00:00:00 EDT 2016},

  month        = {Wed Sep 28 00:00:00 EDT 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcb.6b08567

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 94 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Dynamics of Electrolyte Solutions
journal, October 1980

Wolynes, P. G.
Annual Review of Physical Chemistry, Vol. 31, Issue 1
DOI: 10.1146/annurev.pc.31.100180.002021

Ion transport in solvent-free polymers
journal, January 1988

Ratner, Mark A.; Shriver, Duward F.
Chemical Reviews, Vol. 88, Issue 1
DOI: 10.1021/cr00083a006

Polymer Electrolytes: Ionic Transport Mechanisms and Relaxation Coupling
journal, March 2000

Ratner, Mark A.; Johansson, Patrik; Shriver, Duward F.
MRS Bulletin, Vol. 25, Issue 3
DOI: 10.1557/mrs2000.16

Superionic conductors: Transitions, structures, dynamics
journal, April 1979

Boyce, J. B.; Huberman, B. A.
Physics Reports, Vol. 51, Issue 4
DOI: 10.1016/0370-1573(79)90067-X

Superionics: crystal structures and conduction processes
journal, June 2004

Hull, Stephen
Reports on Progress in Physics, Vol. 67, Issue 7
DOI: 10.1088/0034-4885/67/7/R05

Relationship between Ionic Mobility and Segmental Mobility in Polymers in the Liquid State
journal, September 1972

Sasabe, Hiroyuki; Saito, Shogo
Polymer Journal, Vol. 3, Issue 5
DOI: 10.1295/polymj.3.624

Highly Conductive Polymer Electrolytes Containing Rigid Polymers
journal, September 1998

Wei, Xiangyun; Shriver, Duward F.
Chemistry of Materials, Vol. 10, Issue 9
DOI: 10.1021/cm980170z

Decoupled ion transport in mesomorphic polymer electrolyte glasses
journal, March 2001

Imrie, Corrie T.; Ingram, Malcolm D.
Electrochimica Acta, Vol. 46, Issue 10-11
DOI: 10.1016/S0013-4686(00)00734-9

Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes
journal, February 2012

Wang, Yangyang; Agapov, Alexander L.; Fan, Fei
Physical Review Letters, Vol. 108, Issue 8
DOI: 10.1103/PhysRevLett.108.088303

Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes
journal, August 2014

Wang, Yangyang; Fan, Fei; Agapov, Alexander L.
Polymer, Vol. 55, Issue 16
DOI: 10.1016/j.polymer.2014.06.085

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015

Fan, Fei; Wang, Yangyang; Hong, Tao
Macromolecules, Vol. 48, Issue 13
DOI: 10.1021/acs.macromol.5b00257

Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths
journal, January 2014

Choi, U. Hyeok; Ye, Yuesheng; Salas de la Cruz, David
Macromolecules, Vol. 47, Issue 2
DOI: 10.1021/ma402263y

Design of superionic polymer electrolytes
journal, February 2015

Wang, Yangyang; Sokolov, Alexei P.
Current Opinion in Chemical Engineering, Vol. 7
DOI: 10.1016/j.coche.2014.09.002

Fundamental questions relating to ion conduction in disordered solids
journal, March 2009

Dyre, Jeppe C.; Maass, Philipp; Roling, Bernhard
Reports on Progress in Physics, Vol. 72, Issue 4
DOI: 10.1088/0034-4885/72/4/046501

Dynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide studied by nuclear magnetic resonance dispersion and diffusion
journal, January 2015

Ordikhani Seyedlar, Amin; Stapf, Siegfried; Mattea, Carlos
Physical Chemistry Chemical Physics, Vol. 17, Issue 3
DOI: 10.1039/C4CP04178J

Charge transport and mass transport in imidazolium-based ionic liquids
journal, May 2008

Sangoro, J. R.; Serghei, A.; Naumov, S.
Physical Review E, Vol. 77, Issue 5
DOI: 10.1103/PhysRevE.77.051202

Ionic conductivity and diffusion coefficients of lithium salt polymer electrolytes measured with dielectric spectroscopy
journal, August 2011

Munar, Antoni; Andrio, Andreu; Iserte, Rosa
Journal of Non-Crystalline Solids, Vol. 357, Issue 16-17
DOI: 10.1016/j.jnoncrysol.2011.04.012

Diffusion in ionic liquids: the interplay between molecular structure and dynamics
journal, January 2011

Sangoro, J. R.; Iacob, C.; Naumov, S.
Soft Matter, Vol. 7, Issue 5
DOI: 10.1039/c0sm01404d

Examination of methods to determine free-ion diffusivity and number density from analysis of electrode polarization
journal, April 2013

Wang, Yangyang; Sun, Che-Nan; Fan, Fei
Physical Review E, Vol. 87, Issue 4
DOI: 10.1103/PhysRevE.87.042308

Dynamics in Glass Forming Sulfuric and Nitric Acid Hydrates
journal, October 2013

Frey, M.; Didzoleit, H.; Gainaru, C.
The Journal of Physical Chemistry B, Vol. 117, Issue 40
DOI: 10.1021/jp407588j

Ionic conductivity and relaxations in ZrO2âY2O3 solid solutions
journal, June 1998

Pimenov, A.
Solid State Ionics, Vol. 109, Issue 1-2
DOI: 10.1016/S0167-2738(98)00082-4

Communication: Conductivity enhancement in plastic-crystalline solid-state electrolytes
journal, August 2015

Geirhos, K.; Lunkenheimer, P.; Michl, M.
The Journal of Chemical Physics, Vol. 143, Issue 8
DOI: 10.1063/1.4929554

A simple model of ac hopping conductivity in disordered solids
journal, April 1985

Dyre, Jeppe C.
Physics Letters A, Vol. 108, Issue 9
DOI: 10.1016/0375-9601(85)90039-8

The random free‐energy barrier model for ac conduction in disordered solids
journal, September 1988

Dyre, Jeppe C.
Journal of Applied Physics, Vol. 64, Issue 5
DOI: 10.1063/1.341681

Decoupling charge transport from the structural dynamics in room temperature ionic liquids
journal, September 2011

Griffin, Philip; Agapov, Alexander L.; Kisliuk, Alexander
The Journal of Chemical Physics, Vol. 135, Issue 11
DOI: 10.1063/1.3638269

Interplay Between Hydrophobic Aggregation and Charge Transport in the Ionic Liquid Methyltrioctylammonium Bis(trifluoromethylsulfonyl)imide
journal, January 2014

Griffin, Philip J.; Holt, Adam P.; Wang, Yangyang
The Journal of Physical Chemistry B, Vol. 118, Issue 3
DOI: 10.1021/jp412365n

Equilibrium and Non-Equilibrium Type β-Relaxations: d -Sorbitol versus o -Terphenyl
journal, May 1999

Wagner, Hermann; Richert, Ranko
The Journal of Physical Chemistry B, Vol. 103, Issue 20
DOI: 10.1021/jp9838947

Ionic Transport, Microphase Separation, and Polymer Relaxation in Poly(propylene glycol) and Lithium Perchlorate Mixtures
journal, November 2013

Fan, Fei; Wang, Yangyang; Sokolov, Alexei P.
Macromolecules, Vol. 46, Issue 23
DOI: 10.1021/ma401238k

Use of the Stimulated Echo in NMR Diffusion Studies
journal, March 1970

Tanner, J. E.
The Journal of Chemical Physics, Vol. 52, Issue 5
DOI: 10.1063/1.1673336

Importance of liquid fragility for energy applications of ionic liquids
journal, September 2015

Sippel, P.; Lunkenheimer, P.; Krohns, S.
Scientific Reports, Vol. 5, Issue 1
DOI: 10.1038/srep13922

Carrier Concentrations and Relaxation Spectroscopy: New Information from Scaling Properties of Conductivity Spectra in Ionically Conducting Glasses
journal, March 1997

Roling, B.; Happe, A.; Funke, K.
Physical Review Letters, Vol. 78, Issue 11
DOI: 10.1103/PhysRevLett.78.2160

Ionic Liquids: Ion Mobilities, Glass Temperatures, and Fragilities
journal, June 2003

Xu, Wu; Cooper, Emanuel I.; Angell, C. Austen
The Journal of Physical Chemistry B, Vol. 107, Issue 25
DOI: 10.1021/jp0275894

Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes
journal, November 2006

Mizuno, F.; Belieres, J. -P.; Kuwata, N.
Journal of Non-Crystalline Solids, Vol. 352, Issue 42-49
DOI: 10.1016/j.jnoncrysol.2006.06.006

Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids
journal, March 1954

Green, Melville S.
The Journal of Chemical Physics, Vol. 22, Issue 3
DOI: 10.1063/1.1740082

Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems
journal, June 1957

Kubo, Ryogo
Journal of the Physical Society of Japan, Vol. 12, Issue 6
DOI: 10.1143/JPSJ.12.570

The haven ratio in fast ionic conductors
journal, October 1982

Murch, G.
Solid State Ionics, Vol. 7, Issue 3
DOI: 10.1016/0167-2738(82)90050-9

Haven ratio and correlation effects in diffusion in li ₃ N
journal, January 1983

Messer, R.; Birli, H.; Schimmele, L.
Radiation Effects, Vol. 75, Issue 1-4
DOI: 10.1080/00337578308224696

Relaxation and Diffusion in Complex Systems
book, January 2011

Ngai, K. L.
Partially Ordered Systems
DOI: 10.1007/978-1-4419-7649-9

Charge Transport and Glassy Dynamics in Ionic Liquids
journal, November 2011

Sangoro, Joshua R.; Kremer, Friedrich
Accounts of Chemical Research, Vol. 45, Issue 4
DOI: 10.1021/ar2001809

Ion dynamics in glassy ionic conductors: Scaling of mean square displacement of mobile ions
journal, October 2014

Kabi, S.; Ghosh, A.
EPL (Europhysics Letters), Vol. 108, Issue 3
DOI: 10.1209/0295-5075/108/36002

Dynamics of T ₂ G ₂ Helices in Atactic and Syndiotactic Polystyrene: New Evidence from Dielectric Spectroscopy and FTIR
journal, July 2006

Lupaşcu, Veronica; Picken, Stephen J.; Wübbenhorst, Michael
Macromolecules, Vol. 39, Issue 15
DOI: 10.1021/ma0606758

Mobile ion concentrations in solid electrolytes from an analysis of a.c. conductivity
journal, December 1983

Almond, D.; West, A.
Solid State Ionics, Vol. 9-10
DOI: 10.1016/0167-2738(83)90247-3

Electrode polarization in dielectric measurements: a review
journal, August 2013

Ishai, Paul Ben; Talary, Mark S.; Caduff, Andreas
Measurement Science and Technology, Vol. 24, Issue 10
DOI: 10.1088/0957-0233/24/10/102001

Electrode polarization effects in broadband dielectric spectroscopy
journal, September 2011

Emmert, S.; Wolf, M.; Gulich, R.
The European Physical Journal B, Vol. 83, Issue 2
DOI: 10.1140/epjb/e2011-20439-8

Sur la relaxation d'une charge d'espace
journal, January 1983

Coelho, R.
Revue de Physique Appliquée, Vol. 18, Issue 3
DOI: 10.1051/rphysap:01983001803013700

Theory of ac Space-Charge Polarization Effects in Photoconductors, Semiconductors, and Electrolytes
journal, October 1953

Macdonald, J. Ross
Physical Review, Vol. 92, Issue 1
DOI: 10.1103/PhysRev.92.4

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes
journal, April 2006

Klein, Robert J.; Zhang, Shihai; Dou, Shichen
The Journal of Chemical Physics, Vol. 124, Issue 14
DOI: 10.1063/1.2186638

ac Hopping Conduction at Extreme Disorder Takes Place on the Percolating Cluster
journal, July 2008

Schrøder, Thomas B.; Dyre, Jeppe C.
Physical Review Letters, Vol. 101, Issue 2
DOI: 10.1103/PhysRevLett.101.025901

Estimation of the free-charge-carrier concentration in fast-ion conducting ${Na}_{2}$ S- $B_{2}$ $S_{3}$ glasses from an analysis of the frequency-dependent conductivity
journal, November 1994

Hairetdinov, Ernest F.; Uvarov, Nikolai F.; Patel, Hitendra K.
Physical Review B, Vol. 50, Issue 18
DOI: 10.1103/PhysRevB.50.13259

Physical Properties of Ionic Liquids: Database and Evaluation
journal, December 2006

Zhang, Suojiang; Sun, Ning; He, Xuezhong
Journal of Physical and Chemical Reference Data, Vol. 35, Issue 4, p. 1475-1517
DOI: 10.1063/1.2204959

Molecular volumes and the Stokes-Einstein equation
journal, April 1970

Edward, John T.
Journal of Chemical Education, Vol. 47, Issue 4
DOI: 10.1021/ed047p261

Effect of Pressure on Decoupling of Ionic Conductivity from Segmental Dynamics in Polymerized Ionic Liquids
journal, November 2015

Wojnarowska, Z.; Knapik, J.; Jacquemin, J.
Macromolecules, Vol. 48, Issue 23
DOI: 10.1021/acs.macromol.5b02130

Universal Approach for Scaling the ac Conductivity in Ionic Glasses
journal, May 1999

Sidebottom, David L.
Physical Review Letters, Vol. 82, Issue 18
DOI: 10.1103/PhysRevLett.82.3653

Works referencing / citing this record:

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology
journal, June 2019

Münzner, Philipp; Hoffmann, Lars; Böhmer, Roland
The Journal of Chemical Physics, Vol. 150, Issue 23
DOI: 10.1063/1.5100600

Structure and dynamics of short-chain polymerized ionic liquids
journal, July 2019

Wieland, F.; Bocharova, V.; Münzner, P.
The Journal of Chemical Physics, Vol. 151, Issue 3
DOI: 10.1063/1.5109228

Ion transport in polymeric ionic liquids: recent developments and open questions
journal, January 2019

Ganesan, Venkat
Molecular Systems Design & Engineering, Vol. 4, Issue 2
DOI: 10.1039/c8me00114f

Ion Dynamics in Ionic-Liquid-Based Li-Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy
journal, September 2018

Jafta, Charl J.; Bridges, Craig; Haupt, Leon
ChemSusChem, Vol. 11, Issue 19
DOI: 10.1002/cssc.201801321

Local and global dynamics of the viscous ion conductors 2Ca(NO ₃ ) ₂ -3KNO ₃ and 2Ca(NO ₃ ) ₂ -3RbNO ₃ probed by ⁸⁷ Rb nuclear magnetic resonance and shear rheology
journal, May 2019

Beerwerth, Joachim; Bierwirth, S. Peter; Adam, Jens
The Journal of Chemical Physics, Vol. 150, Issue 19
DOI: 10.1063/1.5093973

Ion conduction and relaxation mechanism in ionogels embedded with imidazolium based ionic liquids
journal, October 2019

Pal, P.; Ghosh, A.
Journal of Applied Physics, Vol. 126, Issue 13
DOI: 10.1063/1.5123050

Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing
text, January 2019

Reuter, D.; Binder, C.; Lunkenheimer, P.
arXiv
DOI: 10.48550/arxiv.1902.02207

Similar Records in DOE PAGES and OSTI.GOV collections:

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

Journal Article Kumar, Rajeev ; Mahalik, Jyoti P. ; Bocharova, Vera ; ... - Journal of Chemical Physics

Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes frommore »« less
Cited by 14
https://doi.org/10.1063/1.4975309

Full Text Available
Structure and dynamics of short-chain polymerized ionic liquids

Journal Article Wieland, Felix ; Bocharova, Vera ; Münzner, P. ; ... - Journal of Chemical Physics

Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (M_w) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our work demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the samemore »« less
Cited by 15
https://doi.org/10.1063/1.5109228

Full Text Available
Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

Journal Article Fan, Fei ; Wang, Yangyang ; Hong, Tao ; ... - Macromolecules

Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore »« less
https://doi.org/10.1021/acs.macromol.5b00257
Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

Journal Article Das, S. ; Ghosh, A., E-mail: sspag@iacs.res.in - AIP Advances

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore »« less
https://doi.org/10.1063/1.4913320
Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

Journal Article Pal, P. ; Ghosh, A., E-mail: sspag@iacs.res.in - Journal of Applied Physics

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamicsmore »« less
https://doi.org/10.1063/1.4959985

Similar Records

Title: Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Abstract

Citation Formats

Dynamics of Electrolyte Solutions journal, October 1980

Ion transport in solvent-free polymers journal, January 1988

Polymer Electrolytes: Ionic Transport Mechanisms and Relaxation Coupling journal, March 2000

Superionic conductors: Transitions, structures, dynamics journal, April 1979

Superionics: crystal structures and conduction processes journal, June 2004

Relationship between Ionic Mobility and Segmental Mobility in Polymers in the Liquid State journal, September 1972

Highly Conductive Polymer Electrolytes Containing Rigid Polymers journal, September 1998

Decoupled ion transport in mesomorphic polymer electrolyte glasses journal, March 2001

Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes journal, February 2012

Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes journal, August 2014

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups journal, June 2015

Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths journal, January 2014

Design of superionic polymer electrolytes journal, February 2015

Fundamental questions relating to ion conduction in disordered solids journal, March 2009

Dynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide studied by nuclear magnetic resonance dispersion and diffusion journal, January 2015

Charge transport and mass transport in imidazolium-based ionic liquids journal, May 2008

Ionic conductivity and diffusion coefficients of lithium salt polymer electrolytes measured with dielectric spectroscopy journal, August 2011

Diffusion in ionic liquids: the interplay between molecular structure and dynamics journal, January 2011

Examination of methods to determine free-ion diffusivity and number density from analysis of electrode polarization journal, April 2013

Dynamics in Glass Forming Sulfuric and Nitric Acid Hydrates journal, October 2013

Ionic conductivity and relaxations in ZrO2âY2O3 solid solutions journal, June 1998

Communication: Conductivity enhancement in plastic-crystalline solid-state electrolytes journal, August 2015

A simple model of ac hopping conductivity in disordered solids journal, April 1985

The random free‐energy barrier model for ac conduction in disordered solids journal, September 1988

Decoupling charge transport from the structural dynamics in room temperature ionic liquids journal, September 2011

Interplay Between Hydrophobic Aggregation and Charge Transport in the Ionic Liquid Methyltrioctylammonium Bis(trifluoromethylsulfonyl)imide journal, January 2014

Equilibrium and Non-Equilibrium Type β-Relaxations: d -Sorbitol versus o -Terphenyl journal, May 1999

Ionic Transport, Microphase Separation, and Polymer Relaxation in Poly(propylene glycol) and Lithium Perchlorate Mixtures journal, November 2013

Use of the Stimulated Echo in NMR Diffusion Studies journal, March 1970

Importance of liquid fragility for energy applications of ionic liquids journal, September 2015

Carrier Concentrations and Relaxation Spectroscopy: New Information from Scaling Properties of Conductivity Spectra in Ionically Conducting Glasses journal, March 1997

Ionic Liquids: Ion Mobilities, Glass Temperatures, and Fragilities journal, June 2003

Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes journal, November 2006

Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids journal, March 1954

Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems journal, June 1957

The haven ratio in fast ionic conductors journal, October 1982

Haven ratio and correlation effects in diffusion in li 3 N journal, January 1983

Relaxation and Diffusion in Complex Systems book, January 2011

Charge Transport and Glassy Dynamics in Ionic Liquids journal, November 2011

Ion dynamics in glassy ionic conductors: Scaling of mean square displacement of mobile ions journal, October 2014

Dynamics of T 2 G 2 Helices in Atactic and Syndiotactic Polystyrene: New Evidence from Dielectric Spectroscopy and FTIR journal, July 2006

Mobile ion concentrations in solid electrolytes from an analysis of a.c. conductivity journal, December 1983

Electrode polarization in dielectric measurements: a review journal, August 2013

Electrode polarization effects in broadband dielectric spectroscopy journal, September 2011

Sur la relaxation d'une charge d'espace journal, January 1983

Theory of ac Space-Charge Polarization Effects in Photoconductors, Semiconductors, and Electrolytes journal, October 1953

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes journal, April 2006

ac Hopping Conduction at Extreme Disorder Takes Place on the Percolating Cluster journal, July 2008

Estimation of the free-charge-carrier concentration in fast-ion conducting Na 2 S- B 2 S 3 glasses from an analysis of the frequency-dependent conductivity journal, November 1994

Physical Properties of Ionic Liquids: Database and Evaluation journal, December 2006

Molecular volumes and the Stokes-Einstein equation journal, April 1970

Effect of Pressure on Decoupling of Ionic Conductivity from Segmental Dynamics in Polymerized Ionic Liquids journal, November 2015

Universal Approach for Scaling the ac Conductivity in Ionic Glasses journal, May 1999

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology journal, June 2019

Structure and dynamics of short-chain polymerized ionic liquids journal, July 2019

Ion transport in polymeric ionic liquids: recent developments and open questions journal, January 2019

Ion Dynamics in Ionic-Liquid-Based Li-Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy journal, September 2018

Local and global dynamics of the viscous ion conductors 2Ca(NO 3 ) 2 -3KNO 3 and 2Ca(NO 3 ) 2 -3RbNO 3 probed by 87 Rb nuclear magnetic resonance and shear rheology journal, May 2019

Ion conduction and relaxation mechanism in ionogels embedded with imidazolium based ionic liquids journal, October 2019

Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing text, January 2019

Dynamics of Electrolyte Solutions
journal, October 1980

Ion transport in solvent-free polymers
journal, January 1988

Polymer Electrolytes: Ionic Transport Mechanisms and Relaxation Coupling
journal, March 2000

Superionic conductors: Transitions, structures, dynamics
journal, April 1979

Superionics: crystal structures and conduction processes
journal, June 2004

Relationship between Ionic Mobility and Segmental Mobility in Polymers in the Liquid State
journal, September 1972

Highly Conductive Polymer Electrolytes Containing Rigid Polymers
journal, September 1998

Decoupled ion transport in mesomorphic polymer electrolyte glasses
journal, March 2001

Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes
journal, February 2012

Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes
journal, August 2014

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015

Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths
journal, January 2014

Design of superionic polymer electrolytes
journal, February 2015

Fundamental questions relating to ion conduction in disordered solids
journal, March 2009

Dynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide studied by nuclear magnetic resonance dispersion and diffusion
journal, January 2015

Charge transport and mass transport in imidazolium-based ionic liquids
journal, May 2008

Ionic conductivity and diffusion coefficients of lithium salt polymer electrolytes measured with dielectric spectroscopy
journal, August 2011

Diffusion in ionic liquids: the interplay between molecular structure and dynamics
journal, January 2011

Examination of methods to determine free-ion diffusivity and number density from analysis of electrode polarization
journal, April 2013

Dynamics in Glass Forming Sulfuric and Nitric Acid Hydrates
journal, October 2013

Ionic conductivity and relaxations in ZrO2âY2O3 solid solutions
journal, June 1998

Communication: Conductivity enhancement in plastic-crystalline solid-state electrolytes
journal, August 2015

A simple model of ac hopping conductivity in disordered solids
journal, April 1985

The random free‐energy barrier model for ac conduction in disordered solids
journal, September 1988

Decoupling charge transport from the structural dynamics in room temperature ionic liquids
journal, September 2011

Interplay Between Hydrophobic Aggregation and Charge Transport in the Ionic Liquid Methyltrioctylammonium Bis(trifluoromethylsulfonyl)imide
journal, January 2014

Equilibrium and Non-Equilibrium Type β-Relaxations: d -Sorbitol versus o -Terphenyl
journal, May 1999

Ionic Transport, Microphase Separation, and Polymer Relaxation in Poly(propylene glycol) and Lithium Perchlorate Mixtures
journal, November 2013

Use of the Stimulated Echo in NMR Diffusion Studies
journal, March 1970

Importance of liquid fragility for energy applications of ionic liquids
journal, September 2015

Carrier Concentrations and Relaxation Spectroscopy: New Information from Scaling Properties of Conductivity Spectra in Ionically Conducting Glasses
journal, March 1997

Ionic Liquids: Ion Mobilities, Glass Temperatures, and Fragilities
journal, June 2003

Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes
journal, November 2006

Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids
journal, March 1954

Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems
journal, June 1957

The haven ratio in fast ionic conductors
journal, October 1982

Haven ratio and correlation effects in diffusion in li ₃ N
journal, January 1983

Relaxation and Diffusion in Complex Systems
book, January 2011

Charge Transport and Glassy Dynamics in Ionic Liquids
journal, November 2011

Ion dynamics in glassy ionic conductors: Scaling of mean square displacement of mobile ions
journal, October 2014

Dynamics of T ₂ G ₂ Helices in Atactic and Syndiotactic Polystyrene: New Evidence from Dielectric Spectroscopy and FTIR
journal, July 2006

Mobile ion concentrations in solid electrolytes from an analysis of a.c. conductivity
journal, December 1983

Electrode polarization in dielectric measurements: a review
journal, August 2013

Electrode polarization effects in broadband dielectric spectroscopy
journal, September 2011

Sur la relaxation d'une charge d'espace
journal, January 1983

Theory of ac Space-Charge Polarization Effects in Photoconductors, Semiconductors, and Electrolytes
journal, October 1953

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes
journal, April 2006

ac Hopping Conduction at Extreme Disorder Takes Place on the Percolating Cluster
journal, July 2008

Estimation of the free-charge-carrier concentration in fast-ion conducting ${Na}_{2}$ S- $B_{2}$ $S_{3}$ glasses from an analysis of the frequency-dependent conductivity
journal, November 1994

Physical Properties of Ionic Liquids: Database and Evaluation
journal, December 2006

Molecular volumes and the Stokes-Einstein equation
journal, April 1970

Effect of Pressure on Decoupling of Ionic Conductivity from Segmental Dynamics in Polymerized Ionic Liquids
journal, November 2015

Universal Approach for Scaling the ac Conductivity in Ionic Glasses
journal, May 1999

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology
journal, June 2019

Structure and dynamics of short-chain polymerized ionic liquids
journal, July 2019

Ion transport in polymeric ionic liquids: recent developments and open questions
journal, January 2019

Ion Dynamics in Ionic-Liquid-Based Li-Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy
journal, September 2018

Local and global dynamics of the viscous ion conductors 2Ca(NO ₃ ) ₂ -3KNO ₃ and 2Ca(NO ₃ ) ₂ -3RbNO ₃ probed by ⁸⁷ Rb nuclear magnetic resonance and shear rheology
journal, May 2019

Ion conduction and relaxation mechanism in ionogels embedded with imidazolium based ionic liquids
journal, October 2019

Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing
text, January 2019