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

Roach, David J.; Dou, Shichen; Colby, Ralph H.; Mueller, Karl T.

doi:10.1063/1.3669449

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

Journal Article · Fri Jan 06 04:00:00 UTC 2012 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.3669449 · OSTI ID:1076446

Roach, David J. ^[1]; Dou, Shichen ^[1]; Colby, Ralph H. ^[1]; Mueller, Karl T. ^[2]

Pennsylvania State University, University Park, PA (United States)
Pacific Northwest Lab., Richland, WA (United States). Environmental Molecular Sciences Lab.

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.

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Research Organization:: Pennsylvania State University, University Park, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-07ER46409

OSTI ID:: 1076446

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 136; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

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What do NMR linewidths tell us? Dynamics of alkali cations in a PEO-based nanocomposite polymer electrolyte Wong, Shan; Zax, David B. Electrochimica Acta, Vol. 42, Issue 23-24 https://doi.org/10.1016/s0013-4686(97)00040-6	journal	January 1997
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Ionic Conduction Mechanism of PEO-Type Polymer Electrolytes Investigated by the Carrier Diffusion Phenomenon Using PGSE-NMR Kataoka, Hiroshi; Saito, Yuria; Tabuchi, Masato Macromolecules, Vol. 35, Issue 16 https://doi.org/10.1021/ma012139f	journal	July 2002
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Variable-Temperature ⁷ Li Solid-State NMR Investigation of Li-Ion Mobility and Its Correlation with Conductivity in Pore-Filling Polymer Electrolytes for Secondary Batteries Jeon, Jae-Deok; Kwak, Seung-Yeop Macromolecules, Vol. 39, Issue 23 https://doi.org/10.1021/ma061521v	journal	November 2006
Multi-Length Scale Morphology of Poly(ethylene oxide)-Based Sulfonate Ionomers with Alkali Cations at Room Temperature Wang, Wenqin; Liu, Wenjuan; Tudryn, Gregory J. Macromolecules, Vol. 43, Issue 9 https://doi.org/10.1021/ma100379j	journal	May 2010
Segmental Dynamics and Ion Association in PEO-Based Single Ion Conductors Sinha, Kokonad; Maranas, Janna K. Macromolecules, Vol. 44, Issue 13 https://doi.org/10.1021/ma2005074	journal	July 2011
Molecular Mobility, Ion Mobility, and Mobile Ion Concentration in Poly(ethylene oxide)-Based Polyurethane Ionomers Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H. Macromolecules, Vol. 41, Issue 15 https://doi.org/10.1021/ma800263b	journal	August 2008
An Infrared Spectrocopic Study of a Polyester Copolymer Ionomer Based on Poly(ethylene oxide) Lu, Mingfu; Runt, James; Painter, Paul Macromolecules, Vol. 42, Issue 17 https://doi.org/10.1021/ma900978d	journal	September 2009
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Activation of transport and local dynamics in polysiloxane-based salt-in-polymer electrolytes: a multinuclear NMR study Kunze, Miriam; Karatas, Yunus; Wiemhöfer, Hans-Dieter Physical Chemistry Chemical Physics, Vol. 12, Issue 25 https://doi.org/10.1039/b925840j	journal	January 2010
Correlating the NMR self-diffusion and relaxation measurements with ionic conductivity in polymer electrolytes composed of cross-linked poly(ethylene oxide-propylene oxide) doped with LiN(SO2CF3)2 Hayamizu, Kikuko; Aihara, Yuichi; Price, William S. The Journal of Chemical Physics, Vol. 113, Issue 11 https://doi.org/10.1063/1.1288801	journal	September 2000
Dielectric Relaxation in Glycerol, Propylene Glycol, and n ‐Propanol Davidson, D. W.; Cole, R. H. The Journal of Chemical Physics, Vol. 19, Issue 12 https://doi.org/10.1063/1.1748105	journal	December 1951
Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes Klein, Robert J.; Zhang, Shihai; Dou, Shichen The Journal of Chemical Physics, Vol. 124, Issue 14 https://doi.org/10.1063/1.2186638	journal	April 2006
Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide) Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H. The Journal of Chemical Physics, Vol. 130, Issue 6 https://doi.org/10.1063/1.3063659	journal	February 2009
Nuclear magnetic relaxation study of poly(ethylene oxide)–lithium salt based electrolytes Donoso, J. P.; Bonagamba, T. J.; Panepucci, H. C. The Journal of Chemical Physics, Vol. 98, Issue 12 https://doi.org/10.1063/1.464435	journal	June 1993
Dynamics of sodium ions in NaClO4 complexed in poly(propylene-oxide): A 23Na nuclear magnetic resonance study Chung, S. H.; Jeffrey, K. R.; Stevens, J. R. The Journal of Chemical Physics, Vol. 108, Issue 8 https://doi.org/10.1063/1.475735	journal	February 1998
Relaxation Effects in Nuclear Magnetic Resonance Absorption Bloembergen, N.; Purcell, E. M.; Pound, R. V. Physical Review, Vol. 73, Issue 7 https://doi.org/10.1103/physrev.73.679	journal	April 1948
Cation dynamics and relaxation in nanoscale polymer electrolytes: A 7 Li NMR study Mustarelli, Piercarlo; Capiglia, Claudio; Quartarone, Eliana Physical Review B, Vol. 60, Issue 10 https://doi.org/10.1103/physrevb.60.7228	journal	September 1999
Developments in Polymer Electrolytes for Lithium Batteries Wright, Peter V. MRS Bulletin, Vol. 27, Issue 8 https://doi.org/10.1557/mrs2002.194	journal	August 2002
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
A relationship between NMR cross-polarization rates and dynamic storage modulae of polymers Parker, A. A.; Marcinko, J. J.; Rinaldi, P. Journal of Applied Polymer Science, Vol. 48, Issue 4 https://doi.org/10.1002/app.1993.070480410	journal	April 1993
Calculation of Nuclear Spin Relaxation Times L. Sudmeier, James; E. Anderson, Stanley; S. Frye, James Concepts in Magnetic Resonance, Vol. 2, Issue 4 https://doi.org/10.1002/cmr.1820020403	journal	October 1990
Blockcopolymers - Polyelectrolytes - Biodegradation Bellon-Maurel, V.; Calmon-Decriaud, A.; Chandrasekhar, V. Advances in Polymer Science https://doi.org/10.1007/3-540-69191-X	book	January 1998
Nuclear magnetic resonance and conductivity study of starch based polymer electrolytes Lopes, L. V. S.; Dragunski, D. C.; Pawlicka, A. Electrochimica Acta, Vol. 48, Issue 14-16 https://doi.org/10.1016/S0013-4686(03)00181-6	journal	June 2003
What do NMR linewidths tell us? Dynamics of alkali cations in a PEO-based nanocomposite polymer electrolyte Wong, Shan; Zax, David B. Electrochimica Acta, Vol. 42, Issue 23-24 https://doi.org/10.1016/S0013-4686(97)00040-6	journal	January 1997
Composition effects in polyetherurethane-based solid polymer electrolytes Ng, Simon T. C.; Forsyth, Maria; MacFarlane, Douglas R. Polymer, Vol. 39, Issue 25 https://doi.org/10.1016/S0032-3861(98)00153-0	journal	December 1998
Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers Rikukawa, M.; Sanui, K. Progress in Polymer Science, Vol. 25, Issue 10, p. 1463-1502 https://doi.org/10.1016/S0079-6700(00)00032-0	journal	December 2000
Comparison of lithium-polymer cell performance with unity and nonunity transference numbers Thomas, Karen E.; Sloop, Steve E.; Kerr, John B. Journal of Power Sources, Vol. 89, Issue 2 https://doi.org/10.1016/S0378-7753(00)00420-1	journal	August 2000
Self-doped block copolymer electrolytes for solid-state, rechargeable lithium batteries Sadoway, Donald R.; Huang, Biying; Trapa, Patrick E. Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00642-5	journal	July 2001
Nuclear magnetic resonance study of PEO–chitosan based polymer electrolytes Donoso, J. P.; Lopes, L. V. S.; Pawlicka, A. Electrochimica Acta, Vol. 53, Issue 4 https://doi.org/10.1016/j.electacta.2007.04.101	journal	December 2007
Phase separation and local cation coordination in PEOnLiNTf2 polymer electrolytes: Lessons from solid state NMR Koster, T.; Vanwullen, L. Solid State Ionics, Vol. 178, Issue 37-38 https://doi.org/10.1016/j.ssi.2007.12.019	journal	February 2008
Synthesis and Characterization of Poly(Ethylene Glycol)-Based Single-Ion Conductors Dou, Shichen; Zhang, Shihai; Klein, Robert J. Chemistry of Materials, Vol. 18, Issue 18 https://doi.org/10.1021/cm0603699	journal	September 2006
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Thermally Driven Ionic Aggregation in Poly(ethylene oxide)-Based Sulfonate Ionomers Wang, Wenqin; Tudryn, Gregory J.; Colby, Ralph H. Journal of the American Chemical Society, Vol. 133, Issue 28 https://doi.org/10.1021/ja201405v	journal	July 2011
Ionic Conduction Mechanism of PEO-Type Polymer Electrolytes Investigated by the Carrier Diffusion Phenomenon Using PGSE-NMR Kataoka, Hiroshi; Saito, Yuria; Tabuchi, Masato Macromolecules, Vol. 35, Issue 16 https://doi.org/10.1021/ma012139f	journal	July 2002
Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. Macromolecules, Vol. 39, Issue 4 https://doi.org/10.1021/ma052277v	journal	February 2006
Variable-Temperature ⁷ Li Solid-State NMR Investigation of Li-Ion Mobility and Its Correlation with Conductivity in Pore-Filling Polymer Electrolytes for Secondary Batteries Jeon, Jae-Deok; Kwak, Seung-Yeop Macromolecules, Vol. 39, Issue 23 https://doi.org/10.1021/ma061521v	journal	November 2006
Multi-Length Scale Morphology of Poly(ethylene oxide)-Based Sulfonate Ionomers with Alkali Cations at Room Temperature Wang, Wenqin; Liu, Wenjuan; Tudryn, Gregory J. Macromolecules, Vol. 43, Issue 9 https://doi.org/10.1021/ma100379j	journal	May 2010
Segmental Dynamics and Ion Association in PEO-Based Single Ion Conductors Sinha, Kokonad; Maranas, Janna K. Macromolecules, Vol. 44, Issue 13 https://doi.org/10.1021/ma2005074	journal	July 2011
Molecular Mobility, Ion Mobility, and Mobile Ion Concentration in Poly(ethylene oxide)-Based Polyurethane Ionomers Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H. Macromolecules, Vol. 41, Issue 15 https://doi.org/10.1021/ma800263b	journal	August 2008
An Infrared Spectrocopic Study of a Polyester Copolymer Ionomer Based on Poly(ethylene oxide) Lu, Mingfu; Runt, James; Painter, Paul Macromolecules, Vol. 42, Issue 17 https://doi.org/10.1021/ma900978d	journal	September 2009
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
A facile approach for the preparation of cross-linked sulfonated polyimide membranes for fuel cell application Fang, Jianhua; Zhai, Fengxia; Guo, Xiaoxia J. Mater. Chem., Vol. 17, Issue 11 https://doi.org/10.1039/b613561g	journal	January 2007
Activation of transport and local dynamics in polysiloxane-based salt-in-polymer electrolytes: a multinuclear NMR study Kunze, Miriam; Karatas, Yunus; Wiemhöfer, Hans-Dieter Physical Chemistry Chemical Physics, Vol. 12, Issue 25 https://doi.org/10.1039/b925840j	journal	January 2010
Correlating the NMR self-diffusion and relaxation measurements with ionic conductivity in polymer electrolytes composed of cross-linked poly(ethylene oxide-propylene oxide) doped with LiN(SO2CF3)2 Hayamizu, Kikuko; Aihara, Yuichi; Price, William S. The Journal of Chemical Physics, Vol. 113, Issue 11 https://doi.org/10.1063/1.1288801	journal	September 2000
Dielectric Relaxation in Glycerol, Propylene Glycol, and n ‐Propanol Davidson, D. W.; Cole, R. H. The Journal of Chemical Physics, Vol. 19, Issue 12 https://doi.org/10.1063/1.1748105	journal	December 1951
Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes Klein, Robert J.; Zhang, Shihai; Dou, Shichen The Journal of Chemical Physics, Vol. 124, Issue 14 https://doi.org/10.1063/1.2186638	journal	April 2006
Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide) Fragiadakis, Daniel; Dou, Shichen; Colby, Ralph H. The Journal of Chemical Physics, Vol. 130, Issue 6 https://doi.org/10.1063/1.3063659	journal	February 2009
Nuclear magnetic relaxation study of poly(ethylene oxide)–lithium salt based electrolytes Donoso, J. P.; Bonagamba, T. J.; Panepucci, H. C. The Journal of Chemical Physics, Vol. 98, Issue 12 https://doi.org/10.1063/1.464435	journal	June 1993
Dynamics of sodium ions in NaClO4 complexed in poly(propylene-oxide): A 23Na nuclear magnetic resonance study Chung, S. H.; Jeffrey, K. R.; Stevens, J. R. The Journal of Chemical Physics, Vol. 108, Issue 8 https://doi.org/10.1063/1.475735	journal	February 1998
Relaxation Effects in Nuclear Magnetic Resonance Absorption Bloembergen, N.; Purcell, E. M.; Pound, R. V. Physical Review, Vol. 73, Issue 7 https://doi.org/10.1103/PhysRev.73.679	journal	April 1948
Cation dynamics and relaxation in nanoscale polymer electrolytes: A 7 Li NMR study Mustarelli, Piercarlo; Capiglia, Claudio; Quartarone, Eliana Physical Review B, Vol. 60, Issue 10 https://doi.org/10.1103/PhysRevB.60.7228	journal	September 1999
Developments in Polymer Electrolytes for Lithium Batteries Wright, Peter V. MRS Bulletin, Vol. 27, Issue 8 https://doi.org/10.1557/mrs2002.194	journal	August 2002

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