DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo

Abstract

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.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  3. Univ. of California, Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institute of Standards and Technology (NIST); US Department of Commerce; National Science Foundation (NSF)
OSTI Identifier:
1633251
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Salts; Batteries; Electrolytes; Polymers; Copolymers

Citation Formats

Loo, Whitney S., Faraone, Antonio, Grundy, Lorena S., Gao, Kevin W., and Balsara, Nitash P. Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo. United States: N. p., 2020. Web. doi:10.1021/acsmacrolett.0c00236.
Loo, Whitney S., Faraone, Antonio, Grundy, Lorena S., Gao, Kevin W., & Balsara, Nitash P. Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo. United States. https://doi.org/10.1021/acsmacrolett.0c00236
Loo, Whitney S., Faraone, Antonio, Grundy, Lorena S., Gao, Kevin W., and Balsara, Nitash P. Wed . "Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo". United States. https://doi.org/10.1021/acsmacrolett.0c00236. https://www.osti.gov/servlets/purl/1633251.
@article{osti_1633251,
title = {Polymer Dynamics in Block Copolymer Electrolytes Detected by Neutron Spin Echo},
author = {Loo, Whitney S. and Faraone, Antonio and Grundy, Lorena S. and Gao, Kevin W. and Balsara, Nitash P.},
abstractNote = {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.},
doi = {10.1021/acsmacrolett.0c00236},
journal = {ACS Macro Letters},
number = 5,
volume = 9,
place = {United States},
year = {Wed Apr 15 00:00:00 EDT 2020},
month = {Wed Apr 15 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994

  • Lascaud, S.; Perrier, M.; Vallee, A.
  • Macromolecules, Vol. 27, Issue 25
  • DOI: 10.1021/ma00103a034

An NMR and Ionic Conductivity Study of Ion Dynamics in Liquid Poly(ethylene oxide)-Based Electrolytes Doped with LiN(SO2CF3)2
journal, December 2001

  • Hayamizu, Kikuko; Sugimoto, Kyoko; Akiba, Etsuo
  • The Journal of Physical Chemistry B, Vol. 106, Issue 3
  • DOI: 10.1021/jp013035+

Effect of molecular weight on conductivity of polymer electrolytes
journal, November 2011

  • Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A.
  • Solid State Ionics, Vol. 203, Issue 1
  • DOI: 10.1016/j.ssi.2011.09.021

Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes
journal, July 2019

  • Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B.
  • The Journal of Chemical Physics, Vol. 151, Issue 2
  • DOI: 10.1063/1.5109684

Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes
journal, October 2015


Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups
journal, October 2012


The effect of molecular weight on cation mobility in polymer electrolytes
journal, March 1993


Relaxation in polymer electrolytes on the nanosecond timescale
journal, May 2000

  • Mao, Guomin; Perea, Ricardo Fernandez; Howells, W. Spencer
  • Nature, Vol. 405, Issue 6783
  • DOI: 10.1038/35012032

α-Relaxation in PEO−LiTFSI Polymer Electrolytes
journal, January 2002

  • Mao, Guomin; Saboungi, Marie-Louise; Price, David L.
  • Macromolecules, Vol. 35, Issue 2
  • DOI: 10.1021/ma010108e

Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Ion Transport in Chemically Distinct Polymer Electrolytes
journal, March 2020


Effect of LiClO 4 on the Structure and Mobility of PEO-Based Solid Polymer Electrolytes
journal, March 2009

  • Fullerton-Shirey, Susan K.; Maranas, Janna K.
  • Macromolecules, Vol. 42, Issue 6
  • DOI: 10.1021/ma802502u

Relationship between Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Conductivity in Polymer Electrolytes
journal, March 2018


Globally Suppressed Dynamics in Ion-Doped Polymers
journal, May 2018


Chain and Ion Dynamics in Precise Polyethylene Ionomers
journal, October 2019


Li + Transport in Poly(Ethylene Oxide) Based Electrolytes: Neutron Scattering, Dielectric Spectroscopy, and Molecular Dynamics Simulations
journal, July 2013


Diffusion and migration in polymer electrolytes
journal, April 2020


Role of Solvation on Diffusion of Ions in Diblock Copolymers: Understanding the Molecular Weight Effect through Modeling
journal, October 2019

  • Seo, Youngmi; Shen, Kuan-Hsuan; Brown, Jonathan R.
  • Journal of the American Chemical Society, Vol. 141, Issue 46
  • DOI: 10.1021/jacs.9b07227

Dendrite Growth in Lithium/Polymer Systems
journal, January 2003

  • Monroe, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 150, Issue 10
  • DOI: 10.1149/1.1606686

Quantifying the promise of lithium–air batteries for electric vehicles
journal, January 2014

  • Gallagher, Kevin G.; Goebel, Steven; Greszler, Thomas
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee43870h

Reviving the lithium metal anode for high-energy batteries
journal, March 2017

  • Lin, Dingchang; Liu, Yayuan; Cui, Yi
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2017.16

Comparison of Li + -ion conductivity in linear and crosslinked poly(ethylene oxide)
journal, October 2018

  • Hasan, Nazmul; Pulst, Martin; Samiullah, Muhammad Haris
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 1
  • DOI: 10.1002/polb.24750

Rubbery Block Copolymer Electrolytes for Solid-State Rechargeable Lithium Batteries
journal, January 1999

  • Soo, Philip P.
  • Journal of The Electrochemical Society, Vol. 146, Issue 1
  • DOI: 10.1149/1.1391560

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

  • Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900451e

Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013

  • Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1
  • DOI: 10.1002/polb.23404

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies
journal, January 2020

  • Galluzzo, Michael D.; Loo, Whitney S.; Wang, Andrew A.
  • The Journal of Physical Chemistry B, Vol. 124, Issue 5
  • DOI: 10.1021/acs.jpcb.9b11066

A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers
journal, July 1953

  • Rouse, Prince E.
  • The Journal of Chemical Physics, Vol. 21, Issue 7
  • DOI: 10.1063/1.1699180

Reptation of a Polymer Chain in the Presence of Fixed Obstacles
journal, July 1971

  • de Gennes, P. G.
  • The Journal of Chemical Physics, Vol. 55, Issue 2
  • DOI: 10.1063/1.1675789

Neutron spin echo investigation of the concentration fluctuation dynamics in melts of diblock copolymers
journal, May 1999

  • Montes, H.; Monkenbusch, M.; Willner, L.
  • The Journal of Chemical Physics, Vol. 110, Issue 20
  • DOI: 10.1063/1.478891

Structural Dynamics of Strongly Segregated Block Copolymer Electrolytes
journal, March 2018


Polymers with Complex Architecture by Living Anionic Polymerization
journal, December 2001

  • Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios
  • Chemical Reviews, Vol. 101, Issue 12
  • DOI: 10.1021/cr9901337

Anionic polymerization: High vacuum techniques
journal, January 2000


Composition Dependence of the Flory–Huggins Interaction Parameters of Block Copolymer Electrolytes and the Isotaksis Point
journal, July 2019


Neutron spin-echo investigations on the dynamics of polymers
journal, December 1988


Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering
journal, November 2019


The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology
journal, June 1998

  • Glinka, C. J.; Barker, J. G.; Hammouda, B.
  • Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445
  • DOI: 10.1107/S0021889897017020

Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006


DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt
journal, August 2018

  • Loo, Whitney S.; Galluzzo, Michael D.; Li, Xiuhong
  • The Journal of Physical Chemistry B, Vol. 122, Issue 33
  • DOI: 10.1021/acs.jpcb.8b04189

Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts
journal, October 2010

  • Wanakule, Nisita S.; Virgili, Justin M.; Teran, Alexander A.
  • Macromolecules, Vol. 43, Issue 19
  • DOI: 10.1021/ma1013786

Thermodynamics of Block Copolymers with and without Salt
journal, December 2013

  • Teran, Alexander A.; Balsara, Nitash P.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp408079z

Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter
journal, January 2012


Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers
journal, February 2019

  • Loo, Whitney S.; Balsara, Nitash P.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 18
  • DOI: 10.1002/polb.24800

Neutron Spin Echo in Polymer Systems
book, January 2005

  • Richter, Dieter; Monkenbusch, Michael; Arbe, Arantxa
  • DOI: 10.1007/b106578

Coherent scattering by one reptating chain
journal, January 1981


Chain Dynamics and Viscoelastic Properties of Poly(ethylene oxide)
journal, July 2008

  • Niedzwiedz, K.; Wischnewski, A.; Pyckhout-Hintzen, W.
  • Macromolecules, Vol. 41, Issue 13
  • DOI: 10.1021/ma800446n

Small Particle Driven Chain Disentanglements in Polymer Nanocomposites
journal, April 2017


On the origins of entanglement constraints
journal, July 1993

  • Richter, D.; Farago, B.; Butera, R.
  • Macromolecules, Vol. 26, Issue 4
  • DOI: 10.1021/ma00056a034

Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994

  • Fetters, L. J.; Lohse, D. J.; Richter, D.
  • Macromolecules, Vol. 27, Issue 17
  • DOI: 10.1021/ma00095a001

Rouse and reptation dynamics at finite temperatures: a Monte Carlo simulation
journal, December 1992


Diffusion in microstructured block copolymers: Chain localization and entanglements
journal, October 1993


Mechanisms of Chain Diffusion in Lamellar Block Copolymers
journal, July 1995


Diffusion in microstructured block copolymer melts
journal, August 1997

  • Lodge, Timothy P.; Hamersky, Mark W.; Milhaupt, Jodi M.
  • Macromolecular Symposia, Vol. 121, Issue 1
  • DOI: 10.1002/masy.19971210119

Dynamics of Architecturally Engineered All-Polymer Nanocomposites
journal, October 2018


Effect of Salt Concentration on Ion Clustering and Transport in Polymer Solid Electrolytes: A Molecular Dynamics Study of PEO–LiTFSI
journal, August 2018


Atomistic Description of Ionic Diffusion in PEO–LiTFSI: Effect of Temperature, Molecular Weight, and Ionic Concentration
journal, October 2018


Molecular Dynamics Simulations of Poly(ethylene oxide)/LiI Melts. 1. Structural and Conformational Properties
journal, November 1998

  • Borodin, Oleg; Smith, Grant D.
  • Macromolecules, Vol. 31, Issue 23
  • DOI: 10.1021/ma980838v

Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions
journal, January 2019

  • Gribble, Daniel A.; Frenck, Louise; Shah, Deep B.
  • Journal of The Electrochemical Society, Vol. 166, Issue 14
  • DOI: 10.1149/2.0391914jes

Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions
journal, January 2018

  • Pesko, Danielle M.; Feng, Zhange; Sawhney, Simar
  • Journal of The Electrochemical Society, Vol. 165, Issue 13
  • DOI: 10.1149/2.0921813jes