A poly(ethylene sulfide) backbone is introduced as the main chain of a radical polymer. Anionic ring-opening polymerization of an episulfide monomer substituted with 2,2,6,6tetramethylpiperidin1oxyl (TEMPO), a robust nitroxide radical, yields the corresponding polythioether. Compared to the traditional poly(ethylene oxide) backbone, the new polymer shows a lower glass transition temperature (−10 °C), and about threefold higher solid-state ionic conductivity. The polythioether is also shown to improve the charge/discharge properties of a cathode in solid-state lithium-ion batteries.
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