Rationally Tuning Phase Separation in Polymeric Membranes toward Optimized All-day Passive Radiative Coolers

The all-day passive radiative cooler has emerged as one of the state-of-the-art energy-saving cooling tool kits but routinely suffers from limited processability, high cost, and complicated fabrication processes, which impede large-scale applications. To address these challenges, this work exploits a polymer-based passive radiative cooler with optimized turbidity, reconfigurability, and recyclability. These cooling membranes are fabricated via selective condensation of octyl side chain-modified polyvinyl alcohol through a non-solvent-induced phase separation method. The rational tuning over spatial organization and distribution of the air–polymer interface renders optimized bright whiteness with solar reflectance at 96%. Meanwhile, the abundant −C–O–C– bonds endow such membranes with infrared thermal emittance over 90%. The optimized membrane realizes a subambient cooling of ∼5.7 °C with an average cooling power of ∼81 W m–2 under a solar intensity of ∼528 W m–2. Furthermore, the supramolecule nature of the developed passive radiative cooling membrane bears enhanced shape malleability and recyclability, substantially enhancing its conformability to the complex geometry and extending its life for an eco-friendly society.