Proceedings of 6th International Conference on Hybrid and Organic Photovoltaics (HOPV14)
Publication date: 1st March 2014
Polymer electrolytes offers great advantages in terms of leakage prevention and thermal stability1, but the poor ionic conductivity which occurs in the amorphous phase for the majority of polymer electrolytes is too low to determine an intensive application in most of the electrochemical and photoelectrochemical devices for energy conversion and storage.2 Because of the high flexibility of Si-O bond, high free volume, good thermal and chemical stability and low glass transition temperature, polysiloxanes offer all the necessary prerogatives to play an important role in this field.3 We here report the implementation of a novel class of partially quaternized poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides which have been subjected to a specific cross-linking process to induce the formation of a 3D network and enhance the storage modulus while inducing the delivery of iodide counteranions in the gel. Two different set of polymers have been synthesized by setting two different values of the feed molar ratio between 3-iodopropylmethylsiloxane and dimethylsiloxane units, which are respectively 1:1 and 1:4 and then mixed to a 3-methoxypropionitrile-based solution of iodine (0.15M) and lithium iodide. Six batches of I-/I3--based gel electrolytes were thus formulated and tested by setting three different rates of quaternarization for each polymer. In all the batches the polymer concentration was fixed at 40%. An outstanding improvement of the ionic conductivity (around two orders of magnitude) was revealed as a consequence of the chemical cross-linking, this representing a feasible and cost-effective way to conjugate two basically incompatible prerogatives of a gel electrolyte to be interfaced with a nanostructured electrode for dye solar cells, which are effective pore-filling and long-term stability in harsh environmental conditions.4 A power conversion efficiency superior to 6% as well as an excellent cell’s stability after 1000 hours of light soaking under 0.4 sun have been demonstrated .
Cross linking reaction between aminopropyl terminals of cross-linker and pending iodopropyle groups on the polymer. Ionic conductivity results to be exponentially enhanced once the cross-linking reaction goes on and the viscous electrolytes turn into a solid-state hosting matrix
[1] Wang P. et al Nat. Mater. 2003, 2(7), 498-502 [1] De Gregorio G. et al Chem. Commun. 2012, 48(25), 3109-311 [3] Lewcenko N. A. et al. Chem. Commun. 2008, 33, 3852–3854. [4] De Gregorio G. et al. Macromolecules , under revision
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