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Enhanced ion dissociation of LiCF{sub 3}SO{sub 3} by new carbonate plasticizers: Raman and IR studies

Conference ·
OSTI ID:10117005

The extent of ion dissociation of LiCF{sub 3}SO{sub 3} in propylene carbonate [PC] and new, modified carbonates [MC-3, MC-5] prepared in our laboratory has been determined by Raman spectroscopy. In the modified carbonates the polyether groups -CH{sub 2}(OCH{sub 2}CH{sub 2}){sub n}OCH{sub 3} (n=3 for MC-3 and n=5 for MC-5) replace the 4-CH{sub 3} substituent of PC. The spectra clearly show that both MC-3 and MC-5 promote ion dissociation of the Li triflate salt relative to PC. Furthermore, MC-5 solutions contain more free ions than MC-3 solutions, and are less affected by concentration changes. Infrared spectra demonstrate that Li{sup +} cations associate less with the carbonyl of the modified carbonates than with the carbonyl of PC. These results suggest that the enhanced ion dissociation of Li triflate in MC-3 and MC-5 arises from complexation of the Li{sup +} to the oxygens of the polyether sidechains, and that MC-5 with its six ether oxygens forms the more stable complex.

Research Organization:
Brookhaven National Lab., Upton, NY (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
AC02-76CH00016
OSTI ID:
10117005
Report Number(s):
BNL--48999; CONF-931024--7; ON: DE94005448
Country of Publication:
United States
Language:
English