Miktoarm star copolymers composed of three poly(ethylene oxide) (PEO) arms connected to one polystyrene (PS) chain, i.e., PS-(PEO), demonstrated synergistic improvements in the ionic conductivity and mechanical strength by factors of 2-30 compared to those shown by PS-PEO diblock copolymers. Entropic constraints for the chain stretching of (PEO) gave rise to notably reduced domain sizes of PS-(PEO) electrolytes, compared with the values of PS-PEO analogues. Further, the melting transition of PS-(PEO) with PEO molecular weight of = 2 kg mol was vanished with lithium salt doping at [Li]/[EO] = 0.06 under such confinements, resulting in an order of magnitude increase in the room temperature conductivity. The fact that lithium ion transport in PEO-based copolymers can be tunable by the way PEO chains are connected to hard polymers can lead to innovative designs for solid-state polymer electrolytes.
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