skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers

Abstract

Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though their respective correlation times differ significantly. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments.

Authors:
 [1];  [1];  [1];  [2]
  1. Pennsylvania State University, University Park, PA (United States)
  2. Pacific Northwest Lab., Richland, WA (United States). Environmental Molecular Sciences Lab.
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1076446
Grant/Contract Number:  
FG02-07ER46409
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 136; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Roach, David J., Dou, Shichen, Colby, Ralph H., and Mueller, Karl T. Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers. United States: N. p., 2012. Web. doi:10.1063/1.3669449.
Roach, David J., Dou, Shichen, Colby, Ralph H., & Mueller, Karl T. Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers. United States. doi:10.1063/1.3669449.
Roach, David J., Dou, Shichen, Colby, Ralph H., and Mueller, Karl T. Fri . "Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers". United States. doi:10.1063/1.3669449. https://www.osti.gov/servlets/purl/1076446.
@article{osti_1076446,
title = {Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers},
author = {Roach, David J. and Dou, Shichen and Colby, Ralph H. and Mueller, Karl T.},
abstractNote = {Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though their respective correlation times differ significantly. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments.},
doi = {10.1063/1.3669449},
journal = {Journal of Chemical Physics},
number = 1,
volume = 136,
place = {United States},
year = {2012},
month = {1}
}

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

Citation Metrics:
Cited by: 19 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

Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998


Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers
journal, December 2000


A facile approach for the preparation of cross-linked sulfonated polyimide membranes for fuel cell application
journal, January 2007

  • Fang, Jianhua; Zhai, Fengxia; Guo, Xiaoxia
  • J. Mater. Chem., Vol. 17, Issue 11
  • DOI: 10.1039/b613561g

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Comparison of lithium-polymer cell performance with unity and nonunity transference numbers
journal, August 2000


Self-doped block copolymer electrolytes for solid-state, rechargeable lithium batteries
journal, July 2001


Developments in Polymer Electrolytes for Lithium Batteries
journal, August 2002


Synthesis and Characterization of Poly(Ethylene Glycol)-Based Single-Ion Conductors
journal, September 2006

  • Dou, Shichen; Zhang, Shihai; Klein, Robert J.
  • Chemistry of Materials, Vol. 18, Issue 18
  • DOI: 10.1021/cm0603699

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

Molecular Mobility, Ion Mobility, and Mobile Ion Concentration in Poly(ethylene oxide)-Based Polyurethane Ionomers
journal, August 2008

  • Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H.
  • Macromolecules, Vol. 41, Issue 15
  • DOI: 10.1021/ma800263b

Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide)
journal, February 2009

  • Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H.
  • The Journal of Chemical Physics, Vol. 130, Issue 6
  • DOI: 10.1063/1.3063659

An Infrared Spectrocopic Study of a Polyester Copolymer Ionomer Based on Poly(ethylene oxide)
journal, September 2009

  • Lu, Mingfu; Runt, James; Painter, Paul
  • Macromolecules, Vol. 42, Issue 17
  • DOI: 10.1021/ma900978d

Multi-Length Scale Morphology of Poly(ethylene oxide)-Based Sulfonate Ionomers with Alkali Cations at Room Temperature
journal, May 2010

  • Wang, Wenqin; Liu, Wenjuan; Tudryn, Gregory J.
  • Macromolecules, Vol. 43, Issue 9
  • DOI: 10.1021/ma100379j

Thermally Driven Ionic Aggregation in Poly(ethylene oxide)-Based Sulfonate Ionomers
journal, July 2011

  • Wang, Wenqin; Tudryn, Gregory J.; Colby, Ralph H.
  • Journal of the American Chemical Society, Vol. 133, Issue 28
  • DOI: 10.1021/ja201405v

A relationship between NMR cross-polarization rates and dynamic storage modulae of polymers
journal, April 1993

  • Parker, A. A.; Marcinko, J. J.; Rinaldi, P.
  • Journal of Applied Polymer Science, Vol. 48, Issue 4
  • DOI: 10.1002/app.1993.070480410

Dynamics of sodium ions in NaClO4 complexed in poly(propylene-oxide): A 23Na nuclear magnetic resonance study
journal, February 1998

  • Chung, S. H.; Jeffrey, K. R.; Stevens, J. R.
  • The Journal of Chemical Physics, Vol. 108, Issue 8
  • DOI: 10.1063/1.475735

Nuclear magnetic relaxation study of poly(ethylene oxide)–lithium salt based electrolytes
journal, June 1993

  • Donoso, J. P.; Bonagamba, T. J.; Panepucci, H. C.
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464435

Ionic Conduction Mechanism of PEO-Type Polymer Electrolytes Investigated by the Carrier Diffusion Phenomenon Using PGSE-NMR
journal, July 2002

  • Kataoka, Hiroshi; Saito, Yuria; Tabuchi, Masato
  • Macromolecules, Vol. 35, Issue 16
  • DOI: 10.1021/ma012139f

Phase separation and local cation coordination in PEOnLiNTf2 polymer electrolytes: Lessons from solid state NMR
journal, February 2008


Nuclear magnetic resonance study of PEO–chitosan based polymer electrolytes
journal, December 2007


Composition effects in polyetherurethane-based solid polymer electrolytes
journal, December 1998


What do NMR linewidths tell us? Dynamics of alkali cations in a PEO-based nanocomposite polymer electrolyte
journal, January 1997


Relaxation Effects in Nuclear Magnetic Resonance Absorption
journal, April 1948


Calculation of Nuclear Spin Relaxation Times
journal, October 1990

  • L. Sudmeier, James; E. Anderson, Stanley; S. Frye, James
  • Concepts in Magnetic Resonance, Vol. 2, Issue 4
  • DOI: 10.1002/cmr.1820020403

Activation of transport and local dynamics in polysiloxane-based salt-in-polymer electrolytes: a multinuclear NMR study
journal, January 2010

  • Kunze, Miriam; Karatas, Yunus; Wiemhöfer, Hans-Dieter
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 25
  • DOI: 10.1039/b925840j

Dielectric Relaxation in Glycerol, Propylene Glycol, and n ‐Propanol
journal, December 1951

  • Davidson, D. W.; Cole, R. H.
  • The Journal of Chemical Physics, Vol. 19, Issue 12
  • DOI: 10.1063/1.1748105

Nuclear magnetic resonance and conductivity study of starch based polymer electrolytes
journal, June 2003


Cation dynamics and relaxation in nanoscale polymer electrolytes: A 7 Li NMR study
journal, September 1999

  • Mustarelli, Piercarlo; Capiglia, Claudio; Quartarone, Eliana
  • Physical Review B, Vol. 60, Issue 10
  • DOI: 10.1103/PhysRevB.60.7228

Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations
journal, February 2006

  • Borodin, Oleg; Smith, Grant D.
  • Macromolecules, Vol. 39, Issue 4
  • DOI: 10.1021/ma052277v

Segmental Dynamics and Ion Association in PEO-Based Single Ion Conductors
journal, July 2011

  • Sinha, Kokonad; Maranas, Janna K.
  • Macromolecules, Vol. 44, Issue 13
  • DOI: 10.1021/ma2005074