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Activation of transport and local dynamics in polysiloxane based salt in polymer electrolytes a multinuclear NMR study     
Yazarlar
Miriam Kunze
 Yunus KARATAŞ Yunus KARATAŞ
Ahi Evran Üniversitesi, Türkiye
Hans-Dieter Wiemhöfer
Hellmut Eckert
Monika Schönhoff
Özet
We have investigated a new improved lithium ion conducting salt-in-polymer electrolyte system consisting of a polysiloxane backbone with oligoether side chains and added LiCF3SO3 (LiTf), which has a conductivity at 30°C of up to 1.3 × 10-4 S cm-1 and up to 6.9 × 10-5 S cm-1 after cross-linking, which is employed to enhance mechanical stability. The mechanisms governing local dynamics and mass transport have been studied on the basis of temperature dependent spin-lattice relaxation time and pulsed field gradient diffusion measurements for 7Li, 19F and 1H, respectively. The correlation times characterizing the local ion dynamics reflect the complexation of the cations by the polyether side chains of the polymer and show the anion as the more mobile species. In contrast, 7Li and 19F diffusion coefficients and their activation energies are rather similar, suggesting the formation of ion pairs with similar activation barriers for cation and/or anion long-range transport. In general, the activation energies describing local reorientation are significantly smaller than those characterizing long range diffusion, suggesting that the long-range transport of both cations and anions is a much more complex process than a simple succession of free ion jumps, and involves (1) the coupling of conformational side-chain reorientations to the cation movement, and (2) the correlated diffusion of cations and anions within dimers or clusters. An important practical conclusion from our results is that the relatively high ionic conductivity in polysiloxane-based polymer electrolytes could even be increased if salt dissociation could be enhanced further. © the Owner Societies.
Anahtar Kelimeler
Makale Türü Özgün Makale
Makale Alt Türü SSCI, AHCI, SCI, SCI-Exp dergilerinde yayımlanan tam makale
Dergi Adı Physical Chemistry Chemical Physics
Dergi ISSN 1463-9076
Dergi Tarandığı Indeksler SSCI
Makale Dili İngilizce
Basım Tarihi 01-2010
Cilt No 12
Sayı 25
Sayfalar 6844 / 6851
Doi Numarası 10.1039/B925840J
Makale Linki http://xlink.rsc.org/?DOI=b925840j