Physical‐Entanglements‐Supported Polymeric Form Stable Phase Change Materials with Ultrahigh Melting Enthalpy

Abstract With the rapid development of new energy and the upgrading of electronic devices, structurally stable phase change materials (PCMs) have attracted widespread attentions from both academia and industries. Traditional cross‐linking, composites, or microencapsulation methods for preparation of form stable PCMs usually sacrifice part of the phase change enthalpy and recyclability. Based on the basic polymer viscoelasticity and crystallization theories, here, a kind of novel recyclable polymeric PCM is developed by simple solution mixing ultrahigh molecular weight of polyethylene oxide (UHMWPEO) with its chemical identical oligomer polyethylene glycol (PEG). Rheological and leakage‐proof experiments confirm that, even containing 90% of phase change fraction PEG oligomers, long‐term of structure stability of PCMs can be achieved when the molecular weight of UHMWPEO is higher than 7000 kg mol −1 due to their ultralong terminal relaxation time and large number of entanglements per chain. Furthermore, because of the reduced overall entanglement concentration, phase change enthalpy of PCMs can be greatly promoted, even reaching to ≈185 J g −1 , which is larger than any PEG‐based form stable PCMs in literatures. This work provides a new strategy and mechanism for designing physical‐entanglements‐supported form stable PCMs with ultrahigh phase change enthalpies.