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Amphiphilic polymer gel electrolytes. 4. Ion transport and dynamics as studied by multinuclear pulsed field gradient spin-echo NMR

Gavelin, Patrik LU ; Jannasch, Patric LU ; Furo, Istvan; Pettersson, Erik; Stilbs, Peter; Topgaard, Daniel LU and Söderman, Olle LU (2002) In Macromolecules 35(13). p.5097-5104
Abstract
The transport dynamics in gel electrolytes based on amphiphilic polymers was found to be faster than in gel electrolytes based on corresponding nonamphiphilic polymers. The amphiphilic polymer studied was a polymethacrylate grafted with fluorocarbon and (EO)(9) side chains, and the nonamphiphilic one was a polymethacrylate carrying only (EO)(9) side chains. Self-diffusion coefficients of gel electrolytes based on the two polymers with different contents of 1 M lithium bis(trifluoromethylsulfonyl) imide (LiTFSI) salt in gamma-butyrolactone were determined by H-1, F-19, and Li-7 pulsed field gradient spin-echo NMR spectroscopy. The polymer self-diffusion coefficients showed that the amphiphilic polymer molecules diffused faster than the... (More)
The transport dynamics in gel electrolytes based on amphiphilic polymers was found to be faster than in gel electrolytes based on corresponding nonamphiphilic polymers. The amphiphilic polymer studied was a polymethacrylate grafted with fluorocarbon and (EO)(9) side chains, and the nonamphiphilic one was a polymethacrylate carrying only (EO)(9) side chains. Self-diffusion coefficients of gel electrolytes based on the two polymers with different contents of 1 M lithium bis(trifluoromethylsulfonyl) imide (LiTFSI) salt in gamma-butyrolactone were determined by H-1, F-19, and Li-7 pulsed field gradient spin-echo NMR spectroscopy. The polymer self-diffusion coefficients showed that the amphiphilic polymer molecules diffused faster than the nonamphiphilic ones and seemed more intramolecularly aggregated than intermolecularly. At electrolyte contents above 43 wt %, the ion conductivity of the amphiphilic polymer gel electrolytes was higher than for the corresponding gel based on the nonamphiphilic polymer under identical conditions, as measured by impedance spectroscopy. Moreover, the lithium ion diffusion coefficient in the amphiphilic gel electrolytes was found to be significantly higher than that for corresponding gels based on the nonamphiphilic polymer, The higher ethylene oxide content of the nonamphiphilic polymer decreased the mobility of the lithium ions due to cooperative coordination of lithium ions by ether oxygens in comparison with gamma-BL. The TFSI anion diffusion was however approximately the same in the two gel systems. Consequently, the apparent lithium transference number (taudivided by) of the amphiphilic gels was higher by almost a factor of 3 as compared to that of the gels based on the nonamphiphilic polymer. A splitting of the TFSI signal in the F-19 NMR spectra suggested that the TFSI anions in the amphiphilic polymer gels were partly present in a solvent-rich environment and partly associated with the aggregates formed by the fluorinated side chains. This kind of splitting was not observed in the spectra of the gels based on the nonamphiphilic polymer. The association of TFSI anions to the aggregated fluorinated side chains may thus also play a role in increasing the value of taudivided by for the amphiphilic polymer gels. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
volume
35
issue
13
pages
5097 - 5104
publisher
The American Chemical Society
external identifiers
  • wos:000176215500035
  • scopus:0037129956
ISSN
0024-9297
DOI
10.1021/ma020215o
language
English
LU publication?
yes
id
96c57ab9-6491-4896-be0b-2496e690b641 (old id 150811)
date added to LUP
2007-07-13 11:53:39
date last changed
2017-01-01 04:43:23
@article{96c57ab9-6491-4896-be0b-2496e690b641,
  abstract     = {The transport dynamics in gel electrolytes based on amphiphilic polymers was found to be faster than in gel electrolytes based on corresponding nonamphiphilic polymers. The amphiphilic polymer studied was a polymethacrylate grafted with fluorocarbon and (EO)(9) side chains, and the nonamphiphilic one was a polymethacrylate carrying only (EO)(9) side chains. Self-diffusion coefficients of gel electrolytes based on the two polymers with different contents of 1 M lithium bis(trifluoromethylsulfonyl) imide (LiTFSI) salt in gamma-butyrolactone were determined by H-1, F-19, and Li-7 pulsed field gradient spin-echo NMR spectroscopy. The polymer self-diffusion coefficients showed that the amphiphilic polymer molecules diffused faster than the nonamphiphilic ones and seemed more intramolecularly aggregated than intermolecularly. At electrolyte contents above 43 wt %, the ion conductivity of the amphiphilic polymer gel electrolytes was higher than for the corresponding gel based on the nonamphiphilic polymer under identical conditions, as measured by impedance spectroscopy. Moreover, the lithium ion diffusion coefficient in the amphiphilic gel electrolytes was found to be significantly higher than that for corresponding gels based on the nonamphiphilic polymer, The higher ethylene oxide content of the nonamphiphilic polymer decreased the mobility of the lithium ions due to cooperative coordination of lithium ions by ether oxygens in comparison with gamma-BL. The TFSI anion diffusion was however approximately the same in the two gel systems. Consequently, the apparent lithium transference number (taudivided by) of the amphiphilic gels was higher by almost a factor of 3 as compared to that of the gels based on the nonamphiphilic polymer. A splitting of the TFSI signal in the F-19 NMR spectra suggested that the TFSI anions in the amphiphilic polymer gels were partly present in a solvent-rich environment and partly associated with the aggregates formed by the fluorinated side chains. This kind of splitting was not observed in the spectra of the gels based on the nonamphiphilic polymer. The association of TFSI anions to the aggregated fluorinated side chains may thus also play a role in increasing the value of taudivided by for the amphiphilic polymer gels.},
  author       = {Gavelin, Patrik and Jannasch, Patric and Furo, Istvan and Pettersson, Erik and Stilbs, Peter and Topgaard, Daniel and Söderman, Olle},
  issn         = {0024-9297},
  language     = {eng},
  number       = {13},
  pages        = {5097--5104},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Amphiphilic polymer gel electrolytes. 4. Ion transport and dynamics as studied by multinuclear pulsed field gradient spin-echo NMR},
  url          = {http://dx.doi.org/10.1021/ma020215o},
  volume       = {35},
  year         = {2002},
}