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Transport property and Raman spectroscopic studies of the polymer electrolyte system P(EO){sub n}-NaTFSI

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.1838522· OSTI ID:653261
 [1]; ;  [2]
  1. Umeaa Univ. (Sweden). Dept. of Experimental Physics
  2. Lawrence Berkeley National Lab., CA (United States). Materials Sciences Div.

Concentration dependences of a complete set of ionic transport properties are reported for the binary solid polymeric ion conductor poly(ethylene-oxide) [P(EO)], complexed with NaTFSI, [TFSI = (bis)trifluoromethanesulfonate imide, (CF{sub 3}SO{sub 2}){sub 2}N]. Measured transport properties include the ionic conductivity ({sigma}), the differential salt diffusion coefficient (D{sub s}), and the cationic transference number (t{sub +}{sup 0}). To measure t{sub +}{sup 0}, a recently developed technique based on concentrated solution theory is used. Under this framework no assumptions need to be made concerning ideality of the electrolytic solution. The authors find that for the P(EO){sub n}-NaTFSI complexes the ionic conductivities, and differential salt diffusion coefficients are much higher than those of the previously reported P(EO){sub n}-NaCF{sub 3}SO{sub 3} system. D{sub s} also varies less with complex composition in concentrated solutions. Interestingly, the cationic transference numbers are found to be negative over a wide concentration range, i.e., t{sub +}{sup 0} decreases with increasing salt concentration and reaches a low of {minus}1.15 {+-} 0.25 at a composition corresponding to an ether-oxygen to sodium-ion ratio of 7:1. This implies that the cationic current is mainly carried by complexed ions. Complementary Raman spectroscopic studies directly probing cation-anion and cation-polymer molecular interactions show that extensive interionic interactions occur in this system.

Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
653261
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 5 Vol. 145; ISSN JESOAN; ISSN 0013-4651
Country of Publication:
United States
Language:
English