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Highly Frustrated Poly(ionic liquid) ABC Triblock Terpolymers with Exceptionally High Morphology Factors.

Patrick M LathropRui SunFrederick L BeyerYossef A Elabd
Published in: Macromolecules (2024)
In this work, we report the successful synthesis of 17 unique compositions of a poly(ionic liquid) (PIL) ABC triblock terpolymer, poly(S- b -VBMIm-TFSI- b -HA), where S is styrene, VBMIm-TFSI is vinylbenzyl methylimidazolium bis(trifluoromethanesulfonyl)imide, and HA is hexyl acrylate. Nine distinct morphologies were observed, including two-phase and three-phase disordered microphase separated (D 2 and D 3 ), two-phase hexagonally packed cylinders (C 2 ), core-shell hexagonally packed cylinders (C CS ), three-phase lamellae (L 3 ), two-phase lamellae (L 2 ), core-shell double gyroid (Q 230 ), spheres-in-lamellae (L SI ), and a three-phase hexagonal superlattice of cylinders (C SL ). The L SI morphology was unambiguously confirmed using small-angle X-ray scattering and transmission electron microscopy. Morphology type significantly impacted the ion conductivity of the PIL ABC triblock terpolymers, where remarkable changes in morphology factor (normalized ion conductivity) were observed with only small changes in the conducting volume fraction, i.e., PIL block composition. An exceptionally high morphology factor of 2.0 was observed from the PIL ABC triblock terpolymer with a hexagonal superlattice morphology due to the three-dimensional narrow, continuous PIL nanodomains that accelerate ion conduction. Overall, this work demonstrates the first systematic study of highly frustrated single-ion conducting ABC triblock terpolymers with a diverse set of morphologies and exceptionally high morphology factors, enabling the exploration of transport-morphology relationships to guide the future design of highly conductive polymer electrolytes.
Keyphrases
  • ionic liquid
  • room temperature
  • electron microscopy
  • magnetic resonance imaging
  • magnetic resonance
  • computed tomography
  • reduced graphene oxide