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

Title: Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Abstract

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO4) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO4. At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO4-doped PEOs, for both molecular weights. This work confirms that added salt causes amore » contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [6]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering
  3. Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering; National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Neutron Scattering Div.
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  6. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1777769
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 53; Journal Issue: 16; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; salts; ions; scattering

Citation Formats

Xie, Shuyi, Zhang, Bo, Mao, Yimin, He, Lilin, Hong, Kunlun, Bates, Frank S., and Lodge, Timothy P.. Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.macromol.0c01194.
Xie, Shuyi, Zhang, Bo, Mao, Yimin, He, Lilin, Hong, Kunlun, Bates, Frank S., & Lodge, Timothy P.. Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications. United States. https://doi.org/10.1021/acs.macromol.0c01194
Xie, Shuyi, Zhang, Bo, Mao, Yimin, He, Lilin, Hong, Kunlun, Bates, Frank S., and Lodge, Timothy P.. Thu . "Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications". United States. https://doi.org/10.1021/acs.macromol.0c01194. https://www.osti.gov/servlets/purl/1777769.
@article{osti_1777769,
title = {Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications},
author = {Xie, Shuyi and Zhang, Bo and Mao, Yimin and He, Lilin and Hong, Kunlun and Bates, Frank S. and Lodge, Timothy P.},
abstractNote = {Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO4) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO4. At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO4-doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.},
doi = {10.1021/acs.macromol.0c01194},
journal = {Macromolecules},
number = 16,
volume = 53,
place = {United States},
year = {2020},
month = {8}
}

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

Save / Share:

Works referenced in this record:

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

Insight into Clustering in Poly(ethylene oxide) Solutions
journal, September 2004

  • Hammouda, Boualem; Ho, Derek L.; Kline, Steve
  • Macromolecules, Vol. 37, Issue 18
  • DOI: 10.1021/ma049623d

SANS from Poly(ethylene oxide)/Water Systems
journal, October 2002

  • Hammouda, B.; Ho, D.; Kline, S.
  • Macromolecules, Vol. 35, Issue 22
  • DOI: 10.1021/ma011657n

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

Clustering of poly(ethylene oxide) in water revisited
journal, November 2002

  • Ho, Derek L.; Hammouda, Boualem; Kline, Steven R.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 41, Issue 1
  • DOI: 10.1002/polb.10340

Lithium solvation in bis(trifluoromethanesulfonyl)imide-based ionic liquids
journal, January 2006

  • Lassègues, Jean-Claude; Grondin, Joseph; Talaga, David
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 48
  • DOI: 10.1039/B615127B

Small-angle scattering of two-phase systems: determination and significance of systematic deviations from Porod's law
journal, February 1971


Poly(ethylene oxide)-based electrolytes for lithium-ion batteries
journal, January 2015

  • Xue, Zhigang; He, Dan; Xie, Xiaolin
  • Journal of Materials Chemistry A, Vol. 3, Issue 38
  • DOI: 10.1039/C5TA03471J

Structural and dynamical characterization of melt PEO–salt mixtures
journal, February 2002

  • Triolo, A.; Lo Celso, F.; Arrighi, V.
  • Physica A: Statistical Mechanics and its Applications, Vol. 304, Issue 1-2
  • DOI: 10.1016/S0378-4371(01)00536-2

Molecular-weight Determination by Light Scattering.
journal, January 1947

  • Debye, P.
  • The Journal of Physical and Colloid Chemistry, Vol. 51, Issue 1
  • DOI: 10.1021/j150451a002

Small‐angle neutron scattering by partially deuterated polymers and their blends
journal, March 1994

  • Balsara, N. P.; Lohse, D. J.; Graessley, W. W.
  • The Journal of Chemical Physics, Vol. 100, Issue 5
  • DOI: 10.1063/1.466325

Laboratory‐scale setup for anionic polymerization under inert atmosphere
journal, February 1995

  • Ndoni, Sokol; Papadakis, Christine M.; Bates, Frank S.
  • Review of Scientific Instruments, Vol. 66, Issue 2
  • DOI: 10.1063/1.1146052

Structural effect of glyme–Li + salt solvate ionic liquids on the conformation of poly(ethylene oxide)
journal, January 2016

  • Chen, Zhengfei; McDonald, Samila; Fitzgerald, Paul A.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 22
  • DOI: 10.1039/C6CP00919K

Ion-containing polymers: new energy & clean water
journal, May 2010


Polarisibility and internuclear distance
journal, January 1942


Coil Dimensions of Poly(ethylene oxide) in an Ionic Liquid by Small-Angle Neutron Scattering
journal, October 2017


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

Complexes of alkali metal ions with poly(ethylene oxide)
journal, November 1973


Phase Behavior of Polystyrene- block -poly(2-vinylpyridine) Copolymers in a Selective Ionic Liquid Solvent
journal, July 2009

  • Virgili, Justin M.; Hexemer, Alexander; Pople, John A.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900483n

Computer simulation of a polymer electrolyte: Lithium iodide in amorphous poly(ethylene oxide)
journal, September 1995

  • Müller‐Plathe, Florian; van Gunsteren, Wilfred F.
  • The Journal of Chemical Physics, Vol. 103, Issue 11
  • DOI: 10.1063/1.470611

Lithium-ion coordination-induced conformational change of PEG chains in ionic-liquid-based electrolytes
journal, January 2020

  • Kamiyama, Yuji; Shibata, Masayuki; Kanzaki, Ryo
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 10
  • DOI: 10.1039/C9CP06717E

What Can We Learn from Ionic Conductivity Measurements in Polymer Electrolytes? A Case Study on Poly(ethylene oxide) (PEO)–NaI and PEO–LiTFSI
journal, February 2012

  • Stolwijk, Nicolaas A.; Wiencierz, Manfred; Heddier, Christian
  • The Journal of Physical Chemistry B, Vol. 116, Issue 10
  • DOI: 10.1021/jp2111956

The static scattering function and optical birefringence of a deformed, ideal polymer chain
journal, December 1991

  • Altenberger, Andrzej R.; Rosa, Epaminondas; Dahler, John S.
  • The Journal of Chemical Physics, Vol. 95, Issue 12
  • DOI: 10.1063/1.461205

Dynamic Light Scattering from Block Copolymer Melts near the Order−Disorder Transition
journal, January 1996


Analytical scattering function of a polydisperse Percus-Yevick fluid with Schulz- ( Γ -) distributed diameters
journal, March 1987


Ion Correlation-Induced Phase Separation in Polyelectrolyte Blends
journal, November 2013

  • Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica
  • ACS Macro Letters, Vol. 2, Issue 11
  • DOI: 10.1021/mz400511r

Dilute Aqueous Poly(ethylene oxide) Solutions:  Clusters and Single Molecules in Thermodynamic Equilibrium
journal, January 1996

  • Polverari, Marco; van de Ven, Theo G. M.
  • The Journal of Physical Chemistry, Vol. 100, Issue 32
  • DOI: 10.1021/jp960215o

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

A small-angle neutron scattering study on poly(ethylene oxide) crystals
journal, March 1978


Incoherent neutron scattering from multi-element materials
journal, April 2011


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

Design and performance of a thermal-neutron double-crystal diffractometer for USANS at NIST
journal, November 2005

  • Barker, J. G.; Glinka, C. J.; Moyer, J. J.
  • Journal of Applied Crystallography, Vol. 38, Issue 6, p. 1004-1011
  • DOI: 10.1107/S0021889805032103

Conformation of poly(ethylene oxide) dissolved in the solvate ionic liquid [Li(G4)]TFSI
journal, January 2015

  • Chen, Zhengfei; FitzGerald, Paul A.; Warr, Gregory G.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 22
  • DOI: 10.1039/C5CP02033F

Small Angle Neutron Scattering from the Highly Interacting Polymer Mixture TMPC/PSd: No Evidence of Spatially Dependent χ Parameter
journal, November 2009

  • Cabral, João T.; Higgins, Julia S.
  • Macromolecules, Vol. 42, Issue 24
  • DOI: 10.1021/ma901516v

Density fluctuations in amorphous and semicrystalline polymers
journal, March 1976

  • Rathje, Jens; Ruland, W.
  • Colloid and Polymer Science, Vol. 254, Issue 3
  • DOI: 10.1007/BF01384035

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

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

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


Effect of Branching and Molecular Weight on Heterogeneous Catalytic Deuterium Exchange in Polyolefins
journal, August 2017


Conformations and Structures of Poly(oxyethylene) Melts from Molecular Dynamics Simulations and Small-Angle Neutron Scattering Experiments
journal, January 1996

  • Smith, Grant D.; Yoon, Do Y.; Jaffe, Richard L.
  • Macromolecules, Vol. 29, Issue 10
  • DOI: 10.1021/ma951621t

Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008

  • Park, Moon Jeong; Balsara, Nitash P.
  • Macromolecules, Vol. 41, Issue 10
  • DOI: 10.1021/ma702733f

Thermodynamics of isotopic polymer mixtures: poly(vinylethylene) and poly(ethylethylene)
journal, April 1988

  • Bates, Frank S.; Fetters, L. J.; Wignall, G. D.
  • Macromolecules, Vol. 21, Issue 4
  • DOI: 10.1021/ma00182a040

Isotope-Induced Quantum-Phase Transitions in the Liquid State
journal, September 1986


Unusual Lower Critical Solution Temperature Phase Behavior of Poly(ethylene oxide) in Ionic Liquids
journal, April 2012

  • Lee, Hau-Nan; Newell, Nakisha; Bai, Zhifeng
  • Macromolecules, Vol. 45, Issue 8
  • DOI: 10.1021/ma300335p

Infrared and Raman study of the PEO-LiTFSI polymer electrolyte
journal, April 1998


Lower Critical Solution Temperature (LCST) Phase Behavior of Poly(ethylene oxide) in Ionic Liquids
journal, June 2010

  • Lee, Hau-Nan; Lodge, Timothy P.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
  • DOI: 10.1021/jz100617t

Electrostatic control of block copolymer morphology
journal, June 2014

  • Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica
  • Nature Materials, Vol. 13, Issue 7
  • DOI: 10.1038/nmat4001

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

Effect of Ionic Liquid Components on the Coil Dimensions of PEO
journal, April 2019