Abstract
Helical-helical polypeptide polymerized ionic liquid block copolymers (PPIL BCPs) are synthesized to investigate the role of helical structure on self-assembly and ionic conductivity. PPIL BCPs, consisting of a cationic polypeptide (PTPLG) with bis(trifluoromethane sulfonimide) (TFSI) counterion and varying lengths connected to a length-fixed neutral poly-(γ-benzyl-(L)-glutamate) (PBLG) block, exhibit stable helical conformations with minimal glass transition (T(g)) variation. Here, we show that increasing PIL composition leads to a transition from poorly ordered to highly ordered lamellar (LAM) structures with the highest PIL content BCP forming a bilayer LAM structure with close-packed helices. This morphology yields a 1.5 order of magnitude higher T(g)- and volume fraction-normalized ionic conductivity and a morphology factor f > 0.8 compared to less ordered BCPs with f < 0.05 and f = 2/3 for ideal lamellae. These results highlight the critical role of helical structure in optimizing ion transport, offering a design strategy for high-performance solid electrolytes.