Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo

Loo, Whitney S.; Faraone, Antonio; Grundy, Lorena S.; Gao, Kevin W.; Balsara, Nitash P.

doi:10.1021/acsmacrolett.0c00236

Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo

Journal Article · Wed Apr 15 00:00:00 EDT 2020 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.0c00236· OSTI ID:1633251

^[1]; Faraone, Antonio ^[2]; ^[1]; ^[1]; ^[3]

Univ. of California, Berkeley, CA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Univ. of California, Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Polymer chain dynamics of a nanostructured block copolymer electrolyte, polystyrene-block-poly(ethylene oxide) (SEO) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, are investigated by neutron spin echo (NSE) spectroscopy on the 0.1–100 ns time scale and analyzed using the Rouse model at short times (t ≤ 10 ns) and the reptation tube model at long times (t ≥ 50 ns). In the Rouse regime, the monomeric friction coefficient increases with increasing salt concentration, as seen previously in homopolymer electrolytes. In the reptation regime, the tube diameters, which represent entanglement constraints, decrease with increasing salt concentration. The normalized longest molecular relaxation time, calculated from the NSE results, increases with increasing salt concentration. We argue that quantifying chain motion in the presence of ions is essential for predicting the behavior of polymer-electrolyte-based batteries operating at large currents.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Institute of Standards and Technology (NIST); National Science Foundation (NSF); US Department of Commerce; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1633251

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 5 Vol. 9; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (62)

Butyllithium-Initiated Anionic Synthesis of Well-Defined Poly(styrene-block-ethylene oxide) Block Copolymers with Potassium Salt Additives Quirk, Roderic P.; Kim, Jungahn; Kausch, Charles Polymer International, Vol. 39, Issue 1, p. 3-10 https://doi.org/10.1002/(SICI)1097-0126(199601)39:1<3::AID-PI436>3.0.CO;2-O	journal	January 1996
Anionic polymerization: High vacuum techniques Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18 https://doi.org/10.1002/1099-0518(20000915)38:18<3211::AID-POLA10>3.0.CO;2-L	journal	January 2000
Diffusion in microstructured block copolymer melts Lodge, Timothy P.; Hamersky, Mark W.; Milhaupt, Jodi M. Macromolecular Symposia, Vol. 121, Issue 1 https://doi.org/10.1002/masy.19971210119	journal	August 1997
Block copolymer electrolytes for rechargeable lithium batteries Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H. Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1 https://doi.org/10.1002/polb.23404	journal	November 2013
Comparison of Li ⁺ -ion conductivity in linear and crosslinked poly(ethylene oxide) Hasan, Nazmul; Pulst, Martin; Samiullah, Muhammad Haris Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 1 https://doi.org/10.1002/polb.24750	journal	October 2018
Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers Loo, Whitney S.; Balsara, Nitash P. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 18 https://doi.org/10.1002/polb.24800	journal	February 2019
Neutron Spin Echo in Polymer Systems Richter, Dieter; Monkenbusch, Michael; Arbe, Arantxa https://doi.org/10.1007/b106578	book	January 2005
The effect of molecular weight on cation mobility in polymer electrolytes Shi, J.; Vincent, C. Solid State Ionics, Vol. 60, Issue 1-3 https://doi.org/10.1016/0167-2738(93)90268-8	journal	March 1993
Diffusion and migration in polymer electrolytes Choo, Youngwoo; Halat, David M.; Villaluenga, Irune Progress in Polymer Science, Vol. 103 https://doi.org/10.1016/j.progpolymsci.2020.101220	journal	April 2020
Effect of molecular weight on conductivity of polymer electrolytes Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A. Solid State Ionics, Vol. 203, Issue 1 https://doi.org/10.1016/j.ssi.2011.09.021	journal	November 2011
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups Devaux, D.; Bouchet, R.; Glé, D. Solid State Ionics, Vol. 227 https://doi.org/10.1016/j.ssi.2012.09.020	journal	October 2012
Effect of Salt Concentration on Ion Clustering and Transport in Polymer Solid Electrolytes: A Molecular Dynamics Study of PEO–LiTFSI Molinari, Nicola; Mailoa, Jonathan P.; Kozinsky, Boris Chemistry of Materials, Vol. 30, Issue 18 https://doi.org/10.1021/acs.chemmater.8b01955	journal	August 2018
Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt Loo, Whitney S.; Galluzzo, Michael D.; Li, Xiuhong The Journal of Physical Chemistry B, Vol. 122, Issue 33 https://doi.org/10.1021/acs.jpcb.8b04189	journal	August 2018
Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies Galluzzo, Michael D.; Loo, Whitney S.; Wang, Andrew A. The Journal of Physical Chemistry B, Vol. 124, Issue 5 https://doi.org/10.1021/acs.jpcb.9b11066	journal	January 2020
Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Ion Transport in Chemically Distinct Polymer Electrolytes Mongcopa, Katrina Irene S.; Gribble, Daniel A.; Loo, Whitney S. Macromolecules, Vol. 53, Issue 7 https://doi.org/10.1021/acs.macromol.0c00091	journal	March 2020
Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes Timachova, Ksenia; Watanabe, Hiroshi; Balsara, Nitash P. Macromolecules, Vol. 48, Issue 21 https://doi.org/10.1021/acs.macromol.5b01724	journal	October 2015
Structural Dynamics of Strongly Segregated Block Copolymer Electrolytes Oparaji, Onyekachi; Narayanan, Suresh; Sandy, Alec Macromolecules, Vol. 51, Issue 7 https://doi.org/10.1021/acs.macromol.7b01803	journal	March 2018
Atomistic Description of Ionic Diffusion in PEO–LiTFSI: Effect of Temperature, Molecular Weight, and Ionic Concentration Brooks, Daniel J.; Merinov, Boris V.; Goddard, William A. Macromolecules, Vol. 51, Issue 21 https://doi.org/10.1021/acs.macromol.8b01753	journal	October 2018
Composition Dependence of the Flory–Huggins Interaction Parameters of Block Copolymer Electrolytes and the Isotaksis Point Loo, Whitney S.; Sethi, Gurmukh K.; Teran, Alexander A. Macromolecules, Vol. 52, Issue 15 https://doi.org/10.1021/acs.macromol.9b00884	journal	July 2019
From Local to Diffusive Dynamics in Polymer Electrolytes: NMR Studies on Coupling of Polymer and Ion Dynamics across Length and Time Scales Becher, Manuel; Becker, Simon; Hecht, Lukas Macromolecules, Vol. 52, Issue 23 https://doi.org/10.1021/acs.macromol.9b01400	journal	November 2019
Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering Loo, Whitney S.; Mongcopa, Katrina I.; Gribble, Daniel A. Macromolecules, Vol. 52, Issue 22 https://doi.org/10.1021/acs.macromol.9b01509	journal	November 2019
Chain and Ion Dynamics in Precise Polyethylene Ionomers Frischknecht, Amalie L.; Paren, Benjamin A.; Middleton, L. Robert Macromolecules, Vol. 52, Issue 20 https://doi.org/10.1021/acs.macromol.9b01712	journal	October 2019
Relationship between Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Conductivity in Polymer Electrolytes Mongcopa, Katrina Irene S.; Tyagi, Madhusudan; Mailoa, Jonathan P. ACS Macro Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acsmacrolett.8b00159	journal	March 2018
Globally Suppressed Dynamics in Ion-Doped Polymers Webb, Michael A.; Yamamoto, Umi; Savoie, Brett M. ACS Macro Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsmacrolett.8b00237	journal	May 2018
Dynamics of Architecturally Engineered All-Polymer Nanocomposites Senses, Erkan; Tyagi, Madhusudan; Pasco, Madeleine ACS Nano, Vol. 12, Issue 11 https://doi.org/10.1021/acsnano.8b02514	journal	October 2018
Polymers with Complex Architecture by Living Anionic Polymerization Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios Chemical Reviews, Vol. 101, Issue 12 https://doi.org/10.1021/cr9901337	journal	December 2001
Role of Solvation on Diffusion of Ions in Diblock Copolymers: Understanding the Molecular Weight Effect through Modeling Seo, Youngmi; Shen, Kuan-Hsuan; Brown, Jonathan R. Journal of the American Chemical Society, Vol. 141, Issue 46 https://doi.org/10.1021/jacs.9b07227	journal	October 2019
An NMR and Ionic Conductivity Study of Ion Dynamics in Liquid Poly(ethylene oxide)-Based Electrolytes Doped with LiN(SO₂CF₃)₂ Hayamizu, Kikuko; Sugimoto, Kyoko; Akiba, Etsuo The Journal of Physical Chemistry B, Vol. 106, Issue 3 https://doi.org/10.1021/jp013035+	journal	December 2001
Thermodynamics of Block Copolymers with and without Salt Teran, Alexander A.; Balsara, Nitash P. The Journal of Physical Chemistry B, Vol. 118, Issue 1 https://doi.org/10.1021/jp408079z	journal	December 2013
Rouse and reptation dynamics at finite temperatures: a Monte Carlo simulation Wittmer, J.; Paul, W.; Binder, K. Macromolecules, Vol. 25, Issue 26 https://doi.org/10.1021/ma00052a023	journal	December 1992
On the origins of entanglement constraints Richter, D.; Farago, B.; Butera, R. Macromolecules, Vol. 26, Issue 4 https://doi.org/10.1021/ma00056a034	journal	July 1993
Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties Fetters, L. J.; Lohse, D. J.; Richter, D. Macromolecules, Vol. 27, Issue 17 https://doi.org/10.1021/ma00095a001	journal	August 1994
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes Lascaud, S.; Perrier, M.; Vallee, A. Macromolecules, Vol. 27, Issue 25 https://doi.org/10.1021/ma00103a034	journal	December 1994
α-Relaxation in PEO−LiTFSI Polymer Electrolytes Mao, Guomin; Saboungi, Marie-Louise; Price, David L. Macromolecules, Vol. 35, Issue 2 https://doi.org/10.1021/ma010108e	journal	January 2002
Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts Wanakule, Nisita S.; Virgili, Justin M.; Teran, Alexander A. Macromolecules, Vol. 43, Issue 19 https://doi.org/10.1021/ma1013786	journal	October 2010
Chain Dynamics and Viscoelastic Properties of Poly(ethylene oxide) Niedzwiedz, K.; Wischnewski, A.; Pyckhout-Hintzen, W. Macromolecules, Vol. 41, Issue 13 https://doi.org/10.1021/ma800446n	journal	July 2008
Effect of LiClO ₄ on the Structure and Mobility of PEO-Based Solid Polymer Electrolytes Fullerton-Shirey, Susan K.; Maranas, Janna K. Macromolecules, Vol. 42, Issue 6 https://doi.org/10.1021/ma802502u	journal	March 2009
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D. Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma900451e	journal	July 2009
Molecular Dynamics Simulations of Poly(ethylene oxide)/LiI Melts. 1. Structural and Conformational Properties Borodin, Oleg; Smith, Grant D. Macromolecules, Vol. 31, Issue 23 https://doi.org/10.1021/ma980838v	journal	November 1998
Relaxation in polymer electrolytes on the nanosecond timescale Mao, Guomin; Perea, Ricardo Fernandez; Howells, W. Spencer Nature, Vol. 405, Issue 6783 https://doi.org/10.1038/35012032	journal	May 2000
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
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
Decoupling segmental relaxation and ionic conductivity for lithium-ion polymer electrolytes Bresser, Dominic; Lyonnard, Sandrine; Iojoiu, Cristina Molecular Systems Design & Engineering, Vol. 4, Issue 4 https://doi.org/10.1039/C9ME00038K	journal	January 2019
Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter Nakamura, Issei; Wang, Zhen-Gang Soft Matter, Vol. 8, Issue 36 https://doi.org/10.1039/c2sm25606a	journal	January 2012
Quantifying the promise of lithium–air batteries for electric vehicles Gallagher, Kevin G.; Goebel, Steven; Greszler, Thomas Energy & Environmental Science, Vol. 7, Issue 5 https://doi.org/10.1039/c3ee43870h	journal	January 2014
Coherent scattering by one reptating chain De Gennes, P. G. Journal de Physique, Vol. 42, Issue 5 https://doi.org/10.1051/jphys:01981004205073500	journal	January 1981
Reptation of a Polymer Chain in the Presence of Fixed Obstacles de Gennes, P. G. The Journal of Chemical Physics, Vol. 55, Issue 2 https://doi.org/10.1063/1.1675789	journal	July 1971
A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers Rouse, Prince E. The Journal of Chemical Physics, Vol. 21, Issue 7 https://doi.org/10.1063/1.1699180	journal	July 1953
Neutron spin echo investigation of the concentration fluctuation dynamics in melts of diblock copolymers Montes, H.; Monkenbusch, M.; Willner, L. The Journal of Chemical Physics, Vol. 110, Issue 20 https://doi.org/10.1063/1.478891	journal	May 1999
Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B. The Journal of Chemical Physics, Vol. 151, Issue 2 https://doi.org/10.1063/1.5109684	journal	July 2019
Li + Transport in Poly(Ethylene Oxide) Based Electrolytes: Neutron Scattering, Dielectric Spectroscopy, and Molecular Dynamics Simulations Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo Physical Review Letters, Vol. 111, Issue 1 https://doi.org/10.1103/PhysRevLett.111.018301	journal	July 2013
Small Particle Driven Chain Disentanglements in Polymer Nanocomposites Senses, Erkan; Ansar, Siyam M.; Kitchens, Christopher L. Physical Review Letters, Vol. 118, Issue 14 https://doi.org/10.1103/PhysRevLett.118.147801	journal	April 2017
Diffusion in microstructured block copolymers: Chain localization and entanglements Dalvi, M. C.; Eastman, C. E.; Lodge, T. P. Physical Review Letters, Vol. 71, Issue 16 https://doi.org/10.1103/PhysRevLett.71.2591	journal	October 1993
Mechanisms of Chain Diffusion in Lamellar Block Copolymers Lodge, T. P.; Dalvi, M. C. Physical Review Letters, Vol. 75, Issue 4 https://doi.org/10.1103/PhysRevLett.75.657	journal	July 1995
Reduction and analysis of SANS and USANS data using IGOR Pro Kline, Steven R. Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900 https://doi.org/10.1107/S0021889806035059	journal	November 2006
Neutron spin-echo investigations on the dynamics of polymers Richter, D.; Ewen, B. Journal of Applied Crystallography, Vol. 21, Issue 6 https://doi.org/10.1107/S002188988800487X	journal	December 1988
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology Glinka, C. J.; Barker, J. G.; Hammouda, B. Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445 https://doi.org/10.1107/S0021889897017020	journal	June 1998
Rubbery Block Copolymer Electrolytes for Solid-State Rechargeable Lithium Batteries Soo, Philip P. Journal of The Electrochemical Society, Vol. 146, Issue 1 https://doi.org/10.1149/1.1391560	journal	January 1999
Dendrite Growth in Lithium/Polymer Systems Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 150, Issue 10 https://doi.org/10.1149/1.1606686	journal	January 2003
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions Gribble, Daniel A.; Frenck, Louise; Shah, Deep B. Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0391914jes	journal	January 2019
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions Pesko, Danielle M.; Feng, Zhange; Sawhney, Simar Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0921813jes	journal	January 2018
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025	journal	November 2009

Similar Records

Molecular Level Differences in Ionic Solvation and Transport Behavior in Ethylene Oxide-Based Homopolymer and Block Copolymer Electrolytes

Journal Article · Sun Feb 21 19:00:00 EST 2021 · Journal of the American Chemical Society · OSTI ID:1821198

Structure and Ionic Conductivity of Polystyrene-block-poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit

Journal Article · Thu Feb 25 19:00:00 EST 2016 · Macromolecules · OSTI ID:1474926

Correlations between Salt-Induced Crystallization, Morphology, Segmental Dynamics, and Conductivity in Amorphous Block Copolymer Electrolytes

Journal Article · Mon Feb 19 19:00:00 EST 2018 · Macromolecules · OSTI ID:1465706

Related Subjects

25 ENERGY STORAGE
Batteries
Copolymers
Electrolytes
Polymers
Salts

Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo

Citation Formats

References (62)

Similar Records

Related Subjects