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Title: On the Mechanism of Ion Transport through Polyphosphazene Solid Polymer Electrolytes 1: NMR, IR, and Raman Spectroscopic Studies and Computational Analysis of 15N Labeled Polyphosphazenes

Abstract

Comprehensive investigation of lithium ion complexation with 15N-labeled polyphosphazenes- 15N-poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene] (15N-MEEP) and 15N-poly-[((2-allylphenoxy)0.12(4-methoxyphenoxy)1.02(2-(2-methoxyethoxy)ethoxy)0.86)phosphazene] (15N-HPP)-was performed by NMR, IR, and Raman spectroscopies. Previous studies characterized the ionic transport through the polymer matrix in terms of "jumps" between neighboring polymer strands utilizing the electron lone pairs of the etherial oxygen nuclei with the nitrogen nuclei on the polyphosphazene backbone not involved. However, noteworthy changes were observed in the NMR, IR, and Raman spectra with the addition of lithium trifluoromethanesulfonate (LiOTf) to the polyphosphazenes. The data indicate that the preferred association for the lithium ion with the polymer is with the nitrogen nuclei, resulting in the formation of a "pocket" with the pendant groups folding around the backbone. NMR temperature-dependent spin-lattice relaxation (T1) studies (13C, 31P, and 15N) indicate significant lithium ion interaction with the backbone nitrogen nuclei. These studies are in agreement with molecular dynamics simulations investigating lithium ion movement within the polyphosphazene matrix.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Idaho National Laboratory (INL)
Sponsoring Org.:
USDOE
OSTI Identifier:
912152
Report Number(s):
INEEL/JOU-00-01514
Journal ID: ISSN 0002-7863; JACSAT; TRN: US0800288
DOE Contract Number:  
DE-AC07-99ID-13727
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 107; Journal Issue: 14; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
99 - GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; ELECTROLYTES; ELECTRONS; LITHIUM; LITHIUM IONS; NITROGEN; NUCLEI; OXYGEN; POLYMERS; RAMAN SPECTRA; SPIN-LATTICE RELAXATION; TRANSPORT; ionic transport; jumps; lithium ion complexation; polymer

Citation Formats

Luther, Thomas Alan, Stewart, Frederick Forrest, Budzien, Joanne Louise, Laviolette, Randall Alexander, Bauer, William Francis, Harrup, Mason Kurt, Allen, Charles Anthony, and Elayan, A. On the Mechanism of Ion Transport through Polyphosphazene Solid Polymer Electrolytes 1: NMR, IR, and Raman Spectroscopic Studies and Computational Analysis of 15N Labeled Polyphosphazenes. United States: N. p., 2003. Web. doi:10.1021/jp027641w.
Luther, Thomas Alan, Stewart, Frederick Forrest, Budzien, Joanne Louise, Laviolette, Randall Alexander, Bauer, William Francis, Harrup, Mason Kurt, Allen, Charles Anthony, & Elayan, A. On the Mechanism of Ion Transport through Polyphosphazene Solid Polymer Electrolytes 1: NMR, IR, and Raman Spectroscopic Studies and Computational Analysis of 15N Labeled Polyphosphazenes. United States. doi:10.1021/jp027641w.
Luther, Thomas Alan, Stewart, Frederick Forrest, Budzien, Joanne Louise, Laviolette, Randall Alexander, Bauer, William Francis, Harrup, Mason Kurt, Allen, Charles Anthony, and Elayan, A. Sat . "On the Mechanism of Ion Transport through Polyphosphazene Solid Polymer Electrolytes 1: NMR, IR, and Raman Spectroscopic Studies and Computational Analysis of 15N Labeled Polyphosphazenes". United States. doi:10.1021/jp027641w.
@article{osti_912152,
title = {On the Mechanism of Ion Transport through Polyphosphazene Solid Polymer Electrolytes 1: NMR, IR, and Raman Spectroscopic Studies and Computational Analysis of 15N Labeled Polyphosphazenes},
author = {Luther, Thomas Alan and Stewart, Frederick Forrest and Budzien, Joanne Louise and Laviolette, Randall Alexander and Bauer, William Francis and Harrup, Mason Kurt and Allen, Charles Anthony and Elayan, A},
abstractNote = {Comprehensive investigation of lithium ion complexation with 15N-labeled polyphosphazenes- 15N-poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene] (15N-MEEP) and 15N-poly-[((2-allylphenoxy)0.12(4-methoxyphenoxy)1.02(2-(2-methoxyethoxy)ethoxy)0.86)phosphazene] (15N-HPP)-was performed by NMR, IR, and Raman spectroscopies. Previous studies characterized the ionic transport through the polymer matrix in terms of "jumps" between neighboring polymer strands utilizing the electron lone pairs of the etherial oxygen nuclei with the nitrogen nuclei on the polyphosphazene backbone not involved. However, noteworthy changes were observed in the NMR, IR, and Raman spectra with the addition of lithium trifluoromethanesulfonate (LiOTf) to the polyphosphazenes. The data indicate that the preferred association for the lithium ion with the polymer is with the nitrogen nuclei, resulting in the formation of a "pocket" with the pendant groups folding around the backbone. NMR temperature-dependent spin-lattice relaxation (T1) studies (13C, 31P, and 15N) indicate significant lithium ion interaction with the backbone nitrogen nuclei. These studies are in agreement with molecular dynamics simulations investigating lithium ion movement within the polyphosphazene matrix.},
doi = {10.1021/jp027641w},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 14,
volume = 107,
place = {United States},
year = {2003},
month = {3}
}