The role of interfacial effects on an ion-conducting poly(styrene-b-ethylene oxide) (PS-b-PEO or SEO) diblock copolymer doped with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was investigated by electrochemical impedance spectroscopy (EIS). Coating the surface of commonly used stainless steel electrodes with a specific random copolymer brush increases the measured ionic conductivity by more than an order of magnitude compared to the uncoated electrodes. The increase in ionic conductivity is related to the interfacial structure of the block copolymer domain morphology on the electrode surface. We show that the impedance associated with the electrode–electrolyte interface can be detected using nonmetallic electrodes, allowing us to distinguish the ionic conductivity behaviors of the bulk electrolyte and the interfacial layers for both as-prepared and annealed samples.
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