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NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN Ferry, Anders, Edman, Ludvig, Forsyth, Maria, MacFarlane, Douglas R. and Sun, Jianzeng 2000, NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN, Electrochimica acta, vol. 45, no. 8-9, pp. 1237-1242. Title NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN Formatted title NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN Author(s) Ferry, Anders Edman, Ludvig Forsyth, Maria MacFarlane, Douglas R. Sun, Jianzeng Journal name Electrochimica acta Volume number 45 Issue number 8-9 Start page 1237 End page 1242 Publisher Elsevier Science Pub. Co. Place of publication New York, N.Y. Publication date 2000-01-03 ISSN 0013-4686 1873-3859 Keyword(s) polymer-in-salt electrolyte lithium and proton NMR FT-Raman spectroscopy poly(acrylonitrile) LiCF3SO3 Summary We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH2CH(CN)]n), and the salt LiCF3SO3 . From NMR studies of the temperature and concentration dependencies of 7Li- and lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li+–PAN interaction. The characteristic δs(CF3) mode of the CF3SO3− anion at ~750–780 cm−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li~60–10:1). A strong Li+–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at ~2244 cm−l in pure PAN, to ~2275 cm−l for Li+-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF3 SO3, the glass transition occurs at progressively lower temperatures. Language eng Field of Research 039999 Chemical Sciences not elsewhere classified Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences HERDC Research category C1.1 Refereed article in a scholarly journal Copyright notice ©2000, Elsevier Science Ltd. Persistent URL http://hdl.handle.net/10536/DRO/DU:30030115 Document type: Journal Article Collection: Institute for Technology Research and Innovation Related Links Link Description Connect to published version (restricted access) Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Versions Version Filter Type Fri, 10 Sep 2010, 15:08:43 EST Tue, 21 Sep 2010, 16:14:33 EST Tue, 21 Sep 2010, 16:16:16 EST Filtered Full Citation counts:   Cited 34 times in TR Web of Science Cited 34 times in Scopus Search Google Scholar Access Statistics: 277 Abstract Views, 0 File Downloads  -  Detailed Statistics Created: Fri, 10 Sep 2010, 15:08:43 EST

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