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Living cationic polymerization is known for a good control over chain growth yielding polymers with well-defined molar mass distributions and low dispersities. However, the practical challenges involved in the synthesis of poly(vinyl ether)s limited suitable post-polymerization modifications (PPM) via chemoselective click reactions. Herein the successful controlled cationic polymerization of vinyl ethers bearing pendant CC double and C≡C triple bonds using a single-component initiation under ambient conditions is reported. Furthermore, the PPM via thiol-ene/-yne and copper(I)-catalyzed alkyne-azide cycloaddition reaction of the obtained polymers is successfully realized laying the foundation for the synthesis of unprecedented functional poly(vinyl ether)s., (© 2021 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

The low melting points of solid polymer electrolytes (SPEs) based on the KTFSI electrolyte salt allow comparatively low operation temperatures (below 50 °C) for K‐ion batteries, unlike their Li or Na counterparts. Unfortunately, for this reason the electrolyte is also rendered mechanically unsuitable in its function to act as a cell separator. Therefore, in this work the use of inorganic nanofillers (Al2O3 and SiO2) is explored with the aim to improve rheological, thermal and cation transport properties of the resulting polymer composite electrolytes. Their electrochemical properties were further examined in K‐metal symmetrical cells and K‐metal/SPE/K2Fe[Fe(CN)6] cells and compared to corresponding liquid electrolyte systems. As a result of particle‐polymer interactions, filler‐containing SPEs showed higher degrees of crystallinity combined with filler polymer interaction and thus improved mechanical integrity in the relevant temperature range of 25–55 °C, while maintaining similar ionic conductivities than a filler‐free sample above the melting temperature. Although plating‐stripping experiments in symmetrical cell setups suggested high cell resistances for various compositions and in some cases even rapid cell failure, Al2O3‐based SPEs generally displayed high capacity retention when cycled against a positive electrode (here Prussian blue analogue K2Fe[Fe(CN)6]) over 100–160 cycles and possibly beyond. [ABSTRACT FROM AUTHOR]