Metal coordination in polymer drives efficient phonon transfer through self-assembled microstructures

Molecular interactions such as hydrogen bond, van der Waals force, covalent bond in association with heat transfer in polymeric materials have been reported, while the relationship between metal-polymer coordination and thermal conduction has not been studied yet. In this work, the molecularly-assembled microstructure of the composites produced by metal coordination with polyvinyl alcohol (PVA) reveals a qualitative correlation between microstructure and thermal conductivity (TC). The ellipsoid-shaped domain and increased coil size create stable phonon transmission channels, which are beneficial for boosting TC by lengthening the mean free path of phonon propagation. Strong coordination between the metal ions and the hydroxyl groups in the polyvinyl alcohol chains results in competition between the inter- and intra-molecular OH–OH hydrogen bonds, which eventually takes precedence. Such coordination structure creates distinctive micro-crystal domains and is discovered to be essential for TC enhancement. Moreover, the power generation value of thermal conversion using PVA-H/2.0Fe(NO₃)₃ film is twice that of pure PVA-H film, which has higher and faster conversion efficiency. These materials have been demonstrated as excellent candidates for improving the conversion efficiency of thermoelectric devices. In summary, this work offers a new strategy for regulating TC through metal coordination and a fundamental comprehension of the link between metal coordination, microstructure, and TC in polymer composites.