Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

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

doi:10.1021/acs.macromol.7b01217

Title: Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

Journal Article · Mon Aug 21 00:00:00 EDT 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.7b01217· OSTI ID:1394356

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^[2]; Fu, Yao ^[3];

^[1]; Carroll, Bobby ^[2];

^[4]; Novikov, Vladimir N. ^[2]; Kisliuk, Alexander M. ^[1];

^[1];

^[2]; Mays, Jimmy W. ^[5];

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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

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.

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

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1394356

Alternate ID(s):: OSTI ID: 1408579

Journal Information:: Macromolecules, Vol. 50, Issue 17; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 73 works

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References (60)

Polymer Electrolytes for Lithium-Ion Batteries Meyer, Wolfgang H. Advanced Materials, Vol. 10, Issue 6, p. 439-448 https://doi.org/10.1002/(SICI)1521-4095(199804)10:6<439::AID-ADMA439>3.0.CO;2-I	journal	April 1998
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Polymer Electrolytes: The Key to Lithium Polymer Batteries Scrosati, B.; Vincent, C. A. MRS Bulletin, Vol. 25, Issue 3 https://doi.org/10.1557/mrs2000.15	journal	March 2000
Recent advances in rechargeable battery materials: a chemist’s perspective Palacín, M. Rosa Chemical Society Reviews, Vol. 38, Issue 9 https://doi.org/10.1039/b820555h	journal	January 2009
Poly(ionic liquid)s: An update Yuan, Jiayin; Mecerreyes, David; Antonietti, Markus Progress in Polymer Science, Vol. 38, Issue 7 https://doi.org/10.1016/j.progpolymsci.2013.04.002	journal	July 2013
Effect of cation structure on the electrochemical and thermal properties of ion conductive polymers obtained from polymerizable ionic liquids Ogihara, Wataru; Washiro, Satoko; Nakajima, Hiromitsu Electrochimica Acta, Vol. 51, Issue 13 https://doi.org/10.1016/j.electacta.2005.07.043	journal	March 2006
Decoupling of ionic conductivity from structural dynamics in polymerized ionic liquids Sangoro, J. R.; Iacob, C.; Agapov, A. L. Soft Matter, Vol. 10, Issue 20 https://doi.org/10.1039/C3SM53202J	journal	January 2014
Effect of Confinement on Polymer Segmental Motion and Ion Mobility in PEO/Layered Silicate Nanocomposites Elmahdy, M. M.; Chrissopoulou, K.; Afratis, A. Macromolecules, Vol. 39, Issue 16 https://doi.org/10.1021/ma0608368	journal	August 2006
Effect of plasticizers on ionic conductivity and dielectric relaxation of PEO-LiClO4 polymer electrolyte Das, S.; Ghosh, A. Electrochimica Acta, Vol. 171 https://doi.org/10.1016/j.electacta.2015.04.178	journal	July 2015
Cationic and dicationic 1,2,3-triazolium-based poly(ethylene glycol ionic liquid)s Obadia, Mona M.; Jourdain, Antoine; Serghei, Anatoli Polymer Chemistry, Vol. 8, Issue 5 https://doi.org/10.1039/C6PY02030E	journal	January 2017
Ion Transport in Glassy Polymer Electrolytes Imrie, C. T.; Ingram, M. D.; McHattie, G. S. The Journal of Physical Chemistry B, Vol. 103, Issue 20 https://doi.org/10.1021/jp983968e	journal	May 1999
Design of superionic polymers—New insights from Walden plot analysis Wang, Yangyang; Fan, Fei; Agapov, Alexander L. Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.026	journal	September 2014
Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes Wang, Yangyang; Fan, Fei; Agapov, Alexander L. Polymer, Vol. 55, Issue 16 https://doi.org/10.1016/j.polymer.2014.06.085	journal	August 2014
Fast ion motion in glassy and amorphous materials Angell, C. Solid State Ionics, Vol. 9-10 https://doi.org/10.1016/0167-2738(83)90206-0	journal	December 1983
New insights from variable-temperature and variable-pressure studies into coupling and decoupling processes for ion transport in polymer electrolytes and glasses Ingram, Malcolm D.; Imrie, Corrie T. Solid State Ionics, Vol. 196, Issue 1 https://doi.org/10.1016/j.ssi.2011.05.019	journal	August 2011
Recent progress on dielectric properties of protic ionic liquids Wojnarowska, Zaneta; Paluch, Marian Journal of Physics: Condensed Matter, Vol. 27, Issue 7 https://doi.org/10.1088/0953-8984/27/7/073202	journal	January 2015
Relationship between Ionic Mobility and Segmental Mobility in Polymers in the Liquid State Sasabe, Hiroyuki; Saito, Shogo Polymer Journal, Vol. 3, Issue 5 https://doi.org/10.1295/polymj.3.624	journal	September 1972
Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes Wang, Yangyang; Agapov, Alexander L.; Fan, Fei Physical Review Letters, Vol. 108, Issue 8 https://doi.org/10.1103/PhysRevLett.108.088303	journal	February 2012
Decoupling Ionic Conductivity from Structural Relaxation: A Way to Solid Polymer Electrolytes? Agapov, A. L.; Sokolov, A. P. Macromolecules, Vol. 44, Issue 11 https://doi.org/10.1021/ma2001096	journal	June 2011
On the Decoupling of Relaxation Modes in a Molecular Liquid Caused by Isothermal Introduction of 2 nm Structural Inhomogeneities Ueno, Kazuhide; Angell, C. Austen The Journal of Physical Chemistry B, Vol. 115, Issue 48 https://doi.org/10.1021/jp111398r	journal	December 2011
Free volume and conductivity in polymer electrolytes Pas, Steven J.; Ingram, Malcolm D.; Funke, Klaus Electrochimica Acta, Vol. 50, Issue 19 https://doi.org/10.1016/j.electacta.2005.02.058	journal	June 2005
Alkyl-Substituted N-Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities Green, Matthew D.; Salas-de la Cruz, David; Ye, Yuesheng Macromolecular Chemistry and Physics, Vol. 212, Issue 23 https://doi.org/10.1002/macp.201100389	journal	October 2011
Optimizing the electrochemical performance of imidazolium-based polymeric ionic liquids by varying tethering groups Jia, Zhe; Yuan, Wen; Sheng, Chunjuan Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 11 https://doi.org/10.1002/pola.27567	journal	March 2015
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
Molecular dynamics simulation of microstructure and counterion transport in dry ionic heteropolymers Wong, Chee; Clarke, Julian H. R. The Journal of Chemical Physics, Vol. 116, Issue 15 https://doi.org/10.1063/1.1461356	journal	April 2002
Molecular dynamics simulation for insight into microscopic mechanism of polymer reinforcement Liu, Jun; Wu, Sizhu; Zhang, Liqun Phys. Chem. Chem. Phys., Vol. 13, Issue 2 https://doi.org/10.1039/C0CP00297F	journal	January 2011
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
Electrode polarization vs. Maxwell-Wagner-Sillars interfacial polarization in dielectric spectra of materials: Characteristic frequencies and scaling laws Samet, M.; Levchenko, V.; Boiteux, G. The Journal of Chemical Physics, Vol. 142, Issue 19 https://doi.org/10.1063/1.4919877	journal	May 2015
A Rayleighian approach for modeling kinetics of ionic transport in polymeric media Kumar, Rajeev; Mahalik, Jyoti P.; Bocharova, Vera The Journal of Chemical Physics, Vol. 146, Issue 6 https://doi.org/10.1063/1.4975309	journal	February 2017
Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths Choi, U. Hyeok; Ye, Yuesheng; Salas de la Cruz, David Macromolecules, Vol. 47, Issue 2 https://doi.org/10.1021/ma402263y	journal	January 2014
Heterogeneous Dynamics of Prototypical Ionic Glass CKN Monitored by Physical Aging Paluch, M.; Wojnarowska, Z.; Hensel-Bielowka, S. Physical Review Letters, Vol. 110, Issue 1 https://doi.org/10.1103/PhysRevLett.110.015702	journal	January 2013
Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems Wojnarowska, Zaneta; Paluch, Krzysztof J.; Shoifet, Evgeni Journal of the American Chemical Society, Vol. 137, Issue 3 https://doi.org/10.1021/ja5103458	journal	January 2015
High Ion Content Siloxane Phosphonium Ionomers with Very Low T _g Liang, Siwei; O’Reilly, Michael V.; Choi, U. Hyeok Macromolecules, Vol. 47, Issue 13 https://doi.org/10.1021/ma5001546	journal	June 2014
Enhanced Ionic Conductivity of a 1,2,3-Triazolium-Based Poly(siloxane ionic liquid) Homopolymer Jourdain, Antoine; Serghei, Anatoli; Drockenmuller, Eric ACS Macro Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsmacrolett.6b00761	journal	October 2016
Why many polymers are so fragile Sokolov, A. P.; Novikov, V. N.; Ding, Y. Journal of Physics: Condensed Matter, Vol. 19, Issue 20 https://doi.org/10.1088/0953-8984/19/20/205116	journal	April 2007
Role of Chemical Structure in Fragility of Polymers: A Qualitative Picture Kunal, Kumar; Robertson, Christopher G.; Pawlus, Sebastian Macromolecules, Vol. 41, Issue 19, p. 7232-7238 https://doi.org/10.1021/ma801155c	journal	October 2008
Effects of backbone rigidity on the local structure and dynamics in polymer melts and glasses Kumar, Rajeev; Goswami, Monojoy; Sumpter, Bobby G. Physical Chemistry Chemical Physics, Vol. 15, Issue 13 https://doi.org/10.1039/c3cp43737j	journal	January 2013
Effect of Pressure on Decoupling of Ionic Conductivity from Segmental Dynamics in Polymerized Ionic Liquids Wojnarowska, Z.; Knapik, J.; Jacquemin, J. Macromolecules, Vol. 48, Issue 23 https://doi.org/10.1021/acs.macromol.5b02130	journal	November 2015
Conductivity Mechanism in Polymerized Imidazolium-Based Protic Ionic Liquid [HSO ₃ –BVIm][OTf]: Dielectric Relaxation Studies Wojnarowska, Z.; Knapik, J.; Díaz, M. Macromolecules, Vol. 47, Issue 12 https://doi.org/10.1021/ma5003479	journal	June 2014
Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups Fan, Fei; Wang, Yangyang; Hong, Tao Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b00257	journal	June 2015
Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers Choi, U. Hyeok; Mittal, Anuj; Price, Terry L. Electrochimica Acta, Vol. 175 https://doi.org/10.1016/j.electacta.2014.12.140	journal	September 2015
Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes Mizuno, F.; Belieres, J. -P.; Kuwata, N. Journal of Non-Crystalline Solids, Vol. 352, Issue 42-49 https://doi.org/10.1016/j.jnoncrysol.2006.06.006	journal	November 2006
Anhydrous Superprotonic Polymer by Superacid Protonation of Cross-linked (PNCl ₂ ) _n Ansari, Younes; Ueno, Kazuhide; Zhao, Zuofeng The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp306302n	journal	January 2013
Ionic conductivity and glass structure Ingram, Malcolm D. Philosophical Magazine B, Vol. 60, Issue 6 https://doi.org/10.1080/13642818908209739	journal	December 1989
High pressure studies of the transport properties of ionic liquids Harris, Kenneth R.; Kanakubo, Mitsuhiro Faraday Discuss., Vol. 154 https://doi.org/10.1039/C1FD00085C	journal	January 2012
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 ] Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter Soft Matter, Vol. 11, Issue 32 https://doi.org/10.1039/C5SM01085C	journal	January 2015
On the scaling behavior of electric conductivity in [C ₄ mim][NTf ₂ ] Wojnarowska, Z.; Jarosz, G.; Grzybowski, A. Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP02253J	journal	January 2014
Experimental evidence of high pressure decoupling between charge transport and structural dynamics in a protic ionic glass-former Wojnarowska, Z.; Rams-Baron, M.; Knapik-Kowalczuk, J. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-07136-5	journal	August 2017
Anomalous properties of the local dynamics in polymer glasses Casalini, R.; Roland, C. M. The Journal of Chemical Physics, Vol. 131, Issue 11 https://doi.org/10.1063/1.3223279	journal	September 2009
Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules Johari, Gyan P.; Goldstein, Martin The Journal of Chemical Physics, Vol. 53, Issue 6 https://doi.org/10.1063/1.1674335	journal	September 1970
Relaxation and Diffusion in Complex Systems Ngai, K. L. Partially Ordered Systems https://doi.org/10.1007/978-1-4419-7649-9	book	January 2011
Molecular Dynamics of Poly(ethylene glycol) and Poly(propylene glycol) Copolymer Networks by Broadband Dielectric Spectroscopy Kalakkunnath, Sumod; Kalika, Douglass S.; Lin, Haiqing Macromolecules, Vol. 40, Issue 8 https://doi.org/10.1021/ma070016a	journal	April 2007
Glass Transition Dynamics of Room-Temperature Ionic Liquid 1-Methyl-3-trimethylsilylmethylimidazolium Tetrafluoroborate Jarosz, Georgina; Mierzwa, Michal; Zioło, Jerzy The Journal of Physical Chemistry B, Vol. 115, Issue 44 https://doi.org/10.1021/jp207291k	journal	November 2011
Study of molecular dynamics of pharmaceutically important protic ionic liquid-verapamil hydrochloride. I. Test of thermodynamic scaling Wojnarowska, Z.; Paluch, M.; Grzybowski, A. The Journal of Chemical Physics, Vol. 131, Issue 10 https://doi.org/10.1063/1.3223540	journal	January 2009
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 Jin, Hui; O'Hare, Bernie; Dong, Jing The Journal of Physical Chemistry B, Vol. 112, Issue 1 https://doi.org/10.1021/jp076462h	journal	January 2008
Pressure and temperature variation of the electrical conductivity of poly(propylene glycol) containing LiCF3SO3 Fontanella, J. J. The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480002	journal	October 1999
Effect of high pressure on electrical relaxation in poly(propylene oxide) and electrical conductivity in poly(propylene oxide) complexed with lithium salts Fontanella, J. J.; Wintersgill, M. C.; Smith, M. K. Journal of Applied Physics, Vol. 60, Issue 8 https://doi.org/10.1063/1.337093	journal	October 1986
NMR, DSC, DMA, and High Pressure Electrical Conductivity Studies in PPO Complexed with Sodium Perchlorate Greenbaum, S. G.; Pak, Y. S.; Wintersgill, M. C. Journal of The Electrochemical Society, Vol. 135, Issue 1 https://doi.org/10.1149/1.2095562	journal	January 1988
Molecular Transport in Liquids and Glasses Cohen, Morrel H.; Turnbull, David The Journal of Chemical Physics, Vol. 31, Issue 5 https://doi.org/10.1063/1.1730566	journal	November 1959

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