Journal
MACROMOLECULES
Volume 45, Issue 17, Pages 7027-7035Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma301036b
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Funding
- U.S. Army Research Office [W911NF-07-1 0452]
- MRSEC Program of the National Science Foundation [DMR11-20901]
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1120901] Funding Source: National Science Foundation
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A series of polymerized ionic liquid (PIL) block and random copolymers were synthesized from an ionic liquid monomer, 1-[(2-methacryloyloxy)ethy1]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (MEBIm-TFSI), and a nonionic monomer, methyl methacrylate (MMA), at various PIL compositions with the goal of understanding the influence of morphology on ion transport. For the diblock copolymers, the partial affinity between the PIL and PMMA blocks resulted in a weakly microphase-separated morphology with no evident long-range periodic structure across the PIL composition range studied, while the random copolymers revealed no microphase separation. These morphologies were identified with a combination of techniques, including differential scanning calorimetry, small-angle X-ray scattering, and transmission electron microscopy. Surprisingly, at similar PIL compositions, the ionic conductivity of the block copolymers were ca. 2 orders of magnitude higher than the random copolymers despite the weak microphase-separated morphology evidenced in the block copolymers. We attribute the higher conductivity in the block copolymers to its microphase-separated morphology, since significant differences in conductivity are still observed even when differences in glass transition temperature are considered. This work demonstrates that local confinement and connectivity of conducting ions in nanoscale ionic domains in PIL block copolymers can accelerate ion transport significantly.
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