Ion transport in helical-helical polypeptide polymerized ionic liquid block copolymers

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 (Tg) 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 Tg- 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. Ion transport in polymers is important for applications in energy devices, but many structures have not been widely considered. Here, the authors report the use of polypeptide ionic liquid block copolymers to investigate the importance of helical secondary structure for ionic conductivity.