NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes

Forsyth, M., Garcia, M., MacFarlane, D. R., Meakin, P., Ng, S. and Smith, M. E. 1996, NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes, Solid state ionics, vol. 85, no. 1-4, pp. 209-218.

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Title NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes
Author(s) Forsyth, M.
Garcia, M.
MacFarlane, D. R.
Meakin, P.
Ng, S.
Smith, M. E.
Journal name Solid state ionics
Volume number 85
Issue number 1-4
Start page 209
End page 218
Publisher Elsevier
Place of publication Amsterdam, The Netherlands
Publication date 1996-05
ISSN 0167-2738
1872-7689
Keyword(s) polymer electrolytes
NMR
plasticizer
ionic structure
Summary Solid polymer electrolytes based on amorphous polyether-urethane networks combined with lithium or sodium salts and a low molecular weight cosolvent (plasticizer) have been investigated in our laboratories for several years. Conductivity enhancements of up to two orders of magnitude can be obtained whilst still retaining solid elastomeric properties. In order to understand the effects of the plasticizers and their mechanism of conductivity enhancement, multinuclear NMR has been employed to investigate ionic structure in polymer electrolyte systems containing NaCF3SO3, LiCF3SO3 and LiClO3 salts.

With increasing dimethyl formamide (DMF) and propylene carbonate (PC) concentration the increasing cation chemical shift with fixed salt concentration indicates a decreasing anion-cation association consistent with an increased number of charge carriers. 13C chemical shift data for the same systems suggests that whilst DMF also decreases cation-polymer interactions, PC does the opposite, presumably by shielding cation-anion interactions. Temperature dependent 7Li spin-lattice relaxation times indicate the expected increase in ionic mobility upon plasticization with a shift of the T1 minimum to lower temperatures. The magnitude of T1 at the minimum increases upon addition of DMF whereas there is a slight decrease when PC is added. This also supports the suggestion that the DMF preferentially solvates the cation whereas the action of PC is limited to coulomb screening, hence freeing the anion.
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 ©1996, Elsevier Science B.V.
Persistent URL http://hdl.handle.net/10536/DRO/DU:30030121

Document type: Journal Article
Collection: Institute for Technology Research and Innovation
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