he superlattice crystals-mimic, flexible/functional ceramic membrane is presented as a new ceramic-driven material/architecture opportunity for next-generation high-performance battery separators. The structural uniqueness/Mn2+-chelating ability of the ceramic membrane (comprising the close-packed, thiol groups-containing silica particles spatially besieged by the polyvinylpyrrolidone/polyacrylonitrile nanofiber skeleton) enables unprecedented improvement in the membrane properties and, more notably, the high-temperature cyclability far beyond those accessible with conventional polymeric separators.