Arun, N and Vasudevan, S and Ramanathan, KV (2003) Li ion transport in an intercalated polymer electrolyte. In: Journal of Chemical Physics, 119 (5). pp. 2840-2848.
Lithium ions solvated by polyethylene-oxide (PEO) have been confined by intercalation within the galleries of an insulating, inorganic layered solid CdPS3. The dc conductivity of this confined polymer electrolyte Cd0.75PS3Li0.5(PEO) displays a distinct change in the mechanism of conduction with temperature, exhibiting a crossover from an Arrhenius temperature dependence at low temperatures to an non-Arrhenius, Vogel–Tamman–Fulcher behavior at higher temperatures. We use 2H, 7Li, and 13C nuclear magnetic resonance (NMR) in combination with infrared spectroscopy to probe Li ion mobility as well as segmental motion of the intercalated PEO. Within the galleries of Cd0.75PS3Li0.5(PEO) both rigid and mobile fractions of the intercalated polymer are present with the equilibrium fraction of the mobile species increasing with temperature. The 7Li (I = 3/2) NMR of the confined polymer electrolyte exhibits an unusual behavior—the appearance of quadrupolar satellites at high temperatures where the conductivity values are appreciable. The results signify the solvation of Li ions by mobile segments of the intercalated PEO. Further proof of this association is seen in the 13C NMR as well as infrared spectra, both of which show evidence of the complexation of Li ions by ether linkages of the interlamellar PEO at high temperature and the absence of such an association at lower temperature when polymer motion is absent.
|Item Type:||Journal Article|
|Additional Information:||Copyright for this article belongs to American Institute of Physics (AIP).|
|Department/Centre:||Division of Chemical Sciences > Sophisticated Instruments Facility
Division of Chemical Sciences > Inorganic & Physical Chemistry
|Date Deposited:||08 Nov 2004|
|Last Modified:||19 Sep 2010 04:17|
Actions (login required)