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Covalently networked polymers offer desirable non-crystallinity and mechanical strength for solid polymer electrolytes (SPEs), but the chemically active cross-links involved in their construction could deteriorate the compatibility with high-energy cathode materials that are electrophilic and/or in the charged state. Herein we reveal a strong dependence of cyclability of such cathodes on the reactivity of covalently networked SPEs and demonstrate a polymer design that renders these SPEs chemically inert. We designed and synthesized two hybrid networks, both with polyethylene oxide as the cation conducting component and polyhedral oligomeric silsesquioxane as the branch point, but respectively use alkylamino and chemically inert triazole groups as cross-links. All-solid-state cells using the alkylamino-containing SPE underwent rapid degradation while cells using triazole SPEs showed stable cycling.more » « less
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