Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies
Abstract
Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing the same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.
- Authors:
-
[1];
[2];
[1];
[4];
[1];
[2];
[6];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
- Univ. of Cincinnati, OH (United States). Department of Aerospace Engineering & Engineering Mechanics
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Computational Sciences & Engineering Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry and Department of Physics and Astronomy
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1394356
- Alternate Identifier(s):
- OSTI ID: 1408579
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 17; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wojnarowska, Zaneta, Feng, Hongbo, Fu, Yao, Cheng, Shiwang, Carroll, Bobby, Kumar, Rajeev, Novikov, Vladimir N., Kisliuk, Alexander M., Saito, Tomonori, Kang, Nam-Goo, Mays, Jimmy W., Sokolov, Alexei P., and Bocharova, Vera. Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies. United States: N. p., 2017.
Web. doi:10.1021/acs.macromol.7b01217.
Wojnarowska, Zaneta, Feng, Hongbo, Fu, Yao, Cheng, Shiwang, Carroll, Bobby, Kumar, Rajeev, Novikov, Vladimir N., Kisliuk, Alexander M., Saito, Tomonori, Kang, Nam-Goo, Mays, Jimmy W., Sokolov, Alexei P., & Bocharova, Vera. Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies. United States. https://doi.org/10.1021/acs.macromol.7b01217
Wojnarowska, Zaneta, Feng, Hongbo, Fu, Yao, Cheng, Shiwang, Carroll, Bobby, Kumar, Rajeev, Novikov, Vladimir N., Kisliuk, Alexander M., Saito, Tomonori, Kang, Nam-Goo, Mays, Jimmy W., Sokolov, Alexei P., and Bocharova, Vera. Mon .
"Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies". United States. https://doi.org/10.1021/acs.macromol.7b01217. https://www.osti.gov/servlets/purl/1394356.
@article{osti_1394356,
title = {Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies},
author = {Wojnarowska, Zaneta and Feng, Hongbo and Fu, Yao and Cheng, Shiwang and Carroll, Bobby and Kumar, Rajeev and Novikov, Vladimir N. and Kisliuk, Alexander M. and Saito, Tomonori and Kang, Nam-Goo and Mays, Jimmy W. and Sokolov, Alexei P. and Bocharova, Vera},
abstractNote = {Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing the same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.},
doi = {10.1021/acs.macromol.7b01217},
journal = {Macromolecules},
number = 17,
volume = 50,
place = {United States},
year = {Mon Aug 21 00:00:00 EDT 2017},
month = {Mon Aug 21 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 73 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998
- Meyer, Wolfgang H.
- Advanced Materials, Vol. 10, Issue 6, p. 439-448
Polymer Electrolytes
journal, July 2013
- Hallinan, Daniel T.; Balsara, Nitash P.
- Annual Review of Materials Research, Vol. 43, Issue 1
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Polymer Electrolytes: The Key to Lithium Polymer Batteries
journal, March 2000
- Scrosati, B.; Vincent, C. A.
- MRS Bulletin, Vol. 25, Issue 3
Recent advances in rechargeable battery materials: a chemist’s perspective
journal, January 2009
- Palacín, M. Rosa
- Chemical Society Reviews, Vol. 38, Issue 9
Poly(ionic liquid)s: An update
journal, July 2013
- Yuan, Jiayin; Mecerreyes, David; Antonietti, Markus
- Progress in Polymer Science, Vol. 38, Issue 7
Effect of cation structure on the electrochemical and thermal properties of ion conductive polymers obtained from polymerizable ionic liquids
journal, March 2006
- Ogihara, Wataru; Washiro, Satoko; Nakajima, Hiromitsu
- Electrochimica Acta, Vol. 51, Issue 13
Decoupling of ionic conductivity from structural dynamics in polymerized ionic liquids
journal, January 2014
- Sangoro, J. R.; Iacob, C.; Agapov, A. L.
- Soft Matter, Vol. 10, Issue 20
Effect of Confinement on Polymer Segmental Motion and Ion Mobility in PEO/Layered Silicate Nanocomposites
journal, August 2006
- Elmahdy, M. M.; Chrissopoulou, K.; Afratis, A.
- Macromolecules, Vol. 39, Issue 16
Effect of plasticizers on ionic conductivity and dielectric relaxation of PEO-LiClO4 polymer electrolyte
journal, July 2015
- Das, S.; Ghosh, A.
- Electrochimica Acta, Vol. 171
Cationic and dicationic 1,2,3-triazolium-based poly(ethylene glycol ionic liquid)s
journal, January 2017
- Obadia, Mona M.; Jourdain, Antoine; Serghei, Anatoli
- Polymer Chemistry, Vol. 8, Issue 5
Ion Transport in Glassy Polymer Electrolytes
journal, May 1999
- Imrie, C. T.; Ingram, M. D.; McHattie, G. S.
- The Journal of Physical Chemistry B, Vol. 103, Issue 20
Design of superionic polymers—New insights from Walden plot analysis
journal, September 2014
- Wang, Yangyang; Fan, Fei; Agapov, Alexander L.
- Solid State Ionics, Vol. 262
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
Fast ion motion in glassy and amorphous materials
journal, December 1983
- Angell, C.
- Solid State Ionics, Vol. 9-10
New insights from variable-temperature and variable-pressure studies into coupling and decoupling processes for ion transport in polymer electrolytes and glasses
journal, August 2011
- Ingram, Malcolm D.; Imrie, Corrie T.
- Solid State Ionics, Vol. 196, Issue 1
Recent progress on dielectric properties of protic ionic liquids
journal, January 2015
- Wojnarowska, Zaneta; Paluch, Marian
- Journal of Physics: Condensed Matter, Vol. 27, Issue 7
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
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
Decoupling Ionic Conductivity from Structural Relaxation: A Way to Solid Polymer Electrolytes?
journal, June 2011
- Agapov, A. L.; Sokolov, A. P.
- Macromolecules, Vol. 44, Issue 11
On the Decoupling of Relaxation Modes in a Molecular Liquid Caused by Isothermal Introduction of 2 nm Structural Inhomogeneities
journal, December 2011
- Ueno, Kazuhide; Angell, C. Austen
- The Journal of Physical Chemistry B, Vol. 115, Issue 48
Free volume and conductivity in polymer electrolytes
journal, June 2005
- Pas, Steven J.; Ingram, Malcolm D.; Funke, Klaus
- Electrochimica Acta, Vol. 50, Issue 19
Alkyl-Substituted N-Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities
journal, October 2011
- Green, Matthew D.; Salas-de la Cruz, David; Ye, Yuesheng
- Macromolecular Chemistry and Physics, Vol. 212, Issue 23
Optimizing the electrochemical performance of imidazolium-based polymeric ionic liquids by varying tethering groups
journal, March 2015
- Jia, Zhe; Yuan, Wen; Sheng, Chunjuan
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 11
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation
journal, April 1990
- Kremer, Kurt; Grest, Gary S.
- The Journal of Chemical Physics, Vol. 92, Issue 8
Molecular dynamics simulation of microstructure and counterion transport in dry ionic heteropolymers
journal, April 2002
- Wong, Chee; Clarke, Julian H. R.
- The Journal of Chemical Physics, Vol. 116, Issue 15
Molecular dynamics simulation for insight into microscopic mechanism of polymer reinforcement
journal, January 2011
- Liu, Jun; Wu, Sizhu; Zhang, Liqun
- Phys. Chem. Chem. Phys., Vol. 13, Issue 2
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Electrode polarization vs. Maxwell-Wagner-Sillars interfacial polarization in dielectric spectra of materials: Characteristic frequencies and scaling laws
journal, May 2015
- Samet, M.; Levchenko, V.; Boiteux, G.
- The Journal of Chemical Physics, Vol. 142, Issue 19
A Rayleighian approach for modeling kinetics of ionic transport in polymeric media
journal, February 2017
- Kumar, Rajeev; Mahalik, Jyoti P.; Bocharova, Vera
- The Journal of Chemical Physics, Vol. 146, Issue 6
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
Heterogeneous Dynamics of Prototypical Ionic Glass CKN Monitored by Physical Aging
journal, January 2013
- Paluch, M.; Wojnarowska, Z.; Hensel-Bielowka, S.
- Physical Review Letters, Vol. 110, Issue 1
Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems
journal, January 2015
- Wojnarowska, Zaneta; Paluch, Krzysztof J.; Shoifet, Evgeni
- Journal of the American Chemical Society, Vol. 137, Issue 3
High Ion Content Siloxane Phosphonium Ionomers with Very Low T g
journal, June 2014
- Liang, Siwei; O’Reilly, Michael V.; Choi, U. Hyeok
- Macromolecules, Vol. 47, Issue 13
Enhanced Ionic Conductivity of a 1,2,3-Triazolium-Based Poly(siloxane ionic liquid) Homopolymer
journal, October 2016
- Jourdain, Antoine; Serghei, Anatoli; Drockenmuller, Eric
- ACS Macro Letters, Vol. 5, Issue 11
Why many polymers are so fragile
journal, April 2007
- Sokolov, A. P.; Novikov, V. N.; Ding, Y.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 20
Role of Chemical Structure in Fragility of Polymers: A Qualitative Picture
journal, October 2008
- Kunal, Kumar; Robertson, Christopher G.; Pawlus, Sebastian
- Macromolecules, Vol. 41, Issue 19, p. 7232-7238
Effects of backbone rigidity on the local structure and dynamics in polymer melts and glasses
journal, January 2013
- Kumar, Rajeev; Goswami, Monojoy; Sumpter, Bobby G.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 13
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
Conductivity Mechanism in Polymerized Imidazolium-Based Protic Ionic Liquid [HSO 3 –BVIm][OTf]: Dielectric Relaxation Studies
journal, June 2014
- Wojnarowska, Z.; Knapik, J.; Díaz, M.
- Macromolecules, Vol. 47, Issue 12
Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015
- Fan, Fei; Wang, Yangyang; Hong, Tao
- Macromolecules, Vol. 48, Issue 13
Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers
journal, September 2015
- Choi, U. Hyeok; Mittal, Anuj; Price, Terry L.
- Electrochimica Acta, Vol. 175
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
Anhydrous Superprotonic Polymer by Superacid Protonation of Cross-linked (PNCl 2 ) n
journal, January 2013
- Ansari, Younes; Ueno, Kazuhide; Zhao, Zuofeng
- The Journal of Physical Chemistry C, Vol. 117, Issue 4
Ionic conductivity and glass structure
journal, December 1989
- Ingram, Malcolm D.
- Philosophical Magazine B, Vol. 60, Issue 6
High pressure studies of the transport properties of ionic liquids
journal, January 2012
- Harris, Kenneth R.; Kanakubo, Mitsuhiro
- Faraday Discuss., Vol. 154
Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C 8 MIM][NTf 2 ]
journal, January 2015
- Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter
- Soft Matter, Vol. 11, Issue 32
On the scaling behavior of electric conductivity in [C 4 mim][NTf 2 ]
journal, January 2014
- Wojnarowska, Z.; Jarosz, G.; Grzybowski, A.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 38
Experimental evidence of high pressure decoupling between charge transport and structural dynamics in a protic ionic glass-former
journal, August 2017
- Wojnarowska, Z.; Rams-Baron, M.; Knapik-Kowalczuk, J.
- Scientific Reports, Vol. 7, Issue 1
Anomalous properties of the local dynamics in polymer glasses
journal, September 2009
- Casalini, R.; Roland, C. M.
- The Journal of Chemical Physics, Vol. 131, Issue 11
Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules
journal, September 1970
- Johari, Gyan P.; Goldstein, Martin
- The Journal of Chemical Physics, Vol. 53, Issue 6
Relaxation and Diffusion in Complex Systems
book, January 2011
- Ngai, K. L.
- Partially Ordered Systems
Molecular Dynamics of Poly(ethylene glycol) and Poly(propylene glycol) Copolymer Networks by Broadband Dielectric Spectroscopy
journal, April 2007
- Kalakkunnath, Sumod; Kalika, Douglass S.; Lin, Haiqing
- Macromolecules, Vol. 40, Issue 8
Glass Transition Dynamics of Room-Temperature Ionic Liquid 1-Methyl-3-trimethylsilylmethylimidazolium Tetrafluoroborate
journal, November 2011
- Jarosz, Georgina; Mierzwa, Michal; Zioło, Jerzy
- The Journal of Physical Chemistry B, Vol. 115, Issue 44
Study of molecular dynamics of pharmaceutically important protic ionic liquid-verapamil hydrochloride. I. Test of thermodynamic scaling
journal, January 2009
- Wojnarowska, Z.; Paluch, M.; Grzybowski, A.
- The Journal of Chemical Physics, Vol. 131, Issue 10
Physical Properties of Ionic Liquids Consisting of the 1-Butyl-3-Methylimidazolium Cation with Various Anions and the Bis(trifluoromethylsulfonyl)imide Anion with Various Cations
journal, January 2008
- Jin, Hui; O'Hare, Bernie; Dong, Jing
- The Journal of Physical Chemistry B, Vol. 112, Issue 1
Pressure and temperature variation of the electrical conductivity of poly(propylene glycol) containing LiCF3SO3
journal, October 1999
- Fontanella, J. J.
- The Journal of Chemical Physics, Vol. 111, Issue 15
Effect of high pressure on electrical relaxation in poly(propylene oxide) and electrical conductivity in poly(propylene oxide) complexed with lithium salts
journal, October 1986
- Fontanella, J. J.; Wintersgill, M. C.; Smith, M. K.
- Journal of Applied Physics, Vol. 60, Issue 8
NMR, DSC, DMA, and High Pressure Electrical Conductivity Studies in PPO Complexed with Sodium Perchlorate
journal, January 1988
- Greenbaum, S. G.; Pak, Y. S.; Wintersgill, M. C.
- Journal of The Electrochemical Society, Vol. 135, Issue 1
Molecular Transport in Liquids and Glasses
journal, November 1959
- Cohen, Morrel H.; Turnbull, David
- The Journal of Chemical Physics, Vol. 31, Issue 5
Works referencing / citing this record:
Ion specific, odd–even glass transition temperatures and conductivities in precise network polymerized ionic liquids
journal, January 2019
- Shen, Chengtian; Zhao, Qiujie; Evans, Christopher M.
- Molecular Systems Design & Engineering, Vol. 4, Issue 2
Structural and Mechanical Properties of Ionic Di-block Copolymers via a Molecular Dynamics Approach
journal, September 2019
- Ma, Mengze; Fu, Yao
- Polymers, Vol. 11, Issue 10
Structural correlations tailor conductive properties in polymerized ionic liquids
journal, January 2019
- Doughty, Benjamin; Genix, Anne-Caroline; Popov, Ivan
- Physical Chemistry Chemical Physics, Vol. 21, Issue 27
Superionic UO 2 : A model anharmonic crystalline material
journal, May 2019
- Zhang, Hao; Wang, Xinyi; Chremos, Alexandros
- The Journal of Chemical Physics, Vol. 150, Issue 17
Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017
- Feng, Hongbo; Lu, Xinyi; Wang, Weiyu
- Polymers, Vol. 9, Issue 12
Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics
journal, April 2018
- Chen, Mingtao; Dugger, Jason W.; Li, Xiuli
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 56, Issue 13
Influence of chain stiffness on the dynamical heterogeneity and fragility of polymer melts
journal, December 2018
- Pan, Deng; Sun, Zhao-Yan
- The Journal of Chemical Physics, Vol. 149, Issue 23
Synthesis of ionic polymers by free radical polymerization using aprotic trimethylsilylmethyl‐substituted monomers
journal, April 2020
- Kaestner, Pia; Strehmel, Veronika
- Journal of Polymer Science, Vol. 58, Issue 7
Decoupling segmental relaxation and ionic conductivity for lithium-ion polymer electrolytes
journal, January 2019
- Bresser, Dominic; Lyonnard, Sandrine; Iojoiu, Cristina
- Molecular Systems Design & Engineering, Vol. 4, Issue 4
Decoupling segmental relaxation and ionic conductivity for lithium-ion polymer electrolytes
text, January 2019
- Bresser, Dominic; Lyonnard, S.; Iojoiu, C.
- Karlsruhe
Activation volume in superpressed glass-formers
journal, September 2019
- Drozd-Rzoska, Aleksandra
- Scientific Reports, Vol. 9, Issue 1
Structural and Mechanical Properties of Ionic Di-block Copolymers via a Molecular Dynamics Approach
journal, September 2019
- Ma, Mengze; Fu, Yao
- Polymers, Vol. 11, Issue 10
Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017
- Feng, Hongbo; Lu, Xinyi; Wang, Weiyu
- Polymers, Vol. 9, Issue 12