Macromolecules
Article
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morphology transition from hexagonally packed cylinders with
1-D conducting pathways to lamellae with 2-D conducting
pathways. It was also observed that the transition into a
coexistence of 2-D lamellae and 3-D network structures
(continuous conducting microdomains) from 2-D lamellar
morphology leads to an additional increase in ionic
conductivity and morphology factor. In fact, in anhydrous
single-ion conducting PIL block copolymers, the coexistence of
2-D lamellae and 3-D network structures at 23.6 PIL mol %
exhibits very high ionic conductivity (0.88 mS cm−1 at 150 °C)
and f = ∼ 1. Additionally, at the similar PIL composition, ionic
conductivity of poly(S-b-AEBIm-TFSI) is more than a half
order of magnitude higher than poly(S-b-VBHIm-TFSI),
demonstrating that an acrylate-based PIL block is more
conductive than a vinylbenzyl-based PIL block and illustrating
the importance of PIL chemistry. These studies of the
morphology and ionic conductivity relationships provide
avenues to design and control the morphologies of solid-state
single-ion conductors for improved properties through careful
selection of their chemistry to control the strength of
microphase separation and their composition and processing
to control the connectivity of the microdomains.
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(26) Carrasco, P. M.; de Luzuriaga, A. R.; Constantinou, M.;
Georgopanos, P.; Rangou, S.; Avgeropoulos, A.; Zafeiropoulos, N. E.;
Grande, H. J.; Cabanero, G.; Mecerreyes, D.; Garcia, I. Macromolecules
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(27) Green, M. D.; Choi, J. H.; Winey, K. I.; Long, T. E.
Macromolecules 2012, 45, 4749.
(28) Weber, R. L.; Ye, Y.; Schmitt, A. L.; Banik, S. M.; Elabd, Y. A.;
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(29) Gu, Y. Y.; Lodge, T. P. Macromolecules 2011, 44, 1732.
(30) Ye, Y.; Choi, J. H.; Winey, K. I.; Elabd, Y. A. Macromolecules
2012, 45, 7027.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR spectra, SEC chromatograms, elemental analysis,
density estimation, 2-D SAXS patterns, ionic conductivity of
PIL homopolymers, and Tg-scaled ionic conductivity of PIL
homopolymers and block copolymers. This material is available
AUTHOR INFORMATION
■
Corresponding Author
(Y.A.E.).
Author Contributions
§J.-H.C. and Y.Y. contributed equally.
Notes
(31) Green, M. D.; Wang, D.; Hemp, S. T.; Choi, J. H.; Winey, K. I.;
The authors declare no competing financial interest.
Heflin, J. R.; Long, T. E. Polymer 2012, 53, 3677.
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ACKNOWLEDGMENTS
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The authors acknowledge the financial support of the U.S.
Army Research Office under Grant W911NF-07-1-0452 Ionic
Liquids in Electro-Active Devices (ILEAD) MURI. We
acknowledge the use of facilities at the University of
Pennsylvania funded in part by the MRSEC Program of the
National Science Foundation (#DMR11-20901).
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dx.doi.org/10.1021/ma400562a | Macromolecules XXXX, XXX, XXX−XXX