Improved Solid Electrolyte Conductivity via Macromolecular Self-Assembly: From Linear to Star Comb-like P(S- co -BzMA)- b -POEGA Block Copolymers.

Star block copolymer electrolytes with a lithium-ion conducting phase are investigated in the present work to assess the influence of this complex architecture compared to that of the linear one, on both, bulk morphology and ionic conductivity. For that purpose, the controlled synthesis of a series of poly(styrene- co -benzyl methacrylate)- b -poly[oligo(ethylene glycol) methyl ether acrylate] [P(S- co -BzMA)- b -POEGA] block copolymers (BCPs) by reversible addition-fragmentation transfer polymerization was performed from either a monofunctional or a tetrafunctional chain transfer agent containing trithiocarbonate groups. We emphasized how a small amount of styrene (6 mol %) drastically improved the control of the RAFT polymerization of benzyl methacrylate mediated by the tetrafunctional chain transfer agent. Transmission electron microscopy and small-angle X-ray scattering demonstrated a clear segregation of the BCPs in the presence of lithium salt. Interestingly, the star BCPs gave rise to highly ordered lamellar structures as compared to that of the linear analogues. Consequently, the reduced lamellae tortuosity of self-assembled star BCPs improved the lithium conductivity by more than 8 times at 30 °C for ∼30 wt % of the POEGA conductive phase.