Thermal energy storage is a promising, sustainable solution for challenging energy management issues. We deploy the fabrication of the reduced graphene oxide (rGO)–polycarbonate (PC) as shell and polyethylene glycol (PEG) as core to obtain hydrophobic phase change electrospun core–shell fiber system for low-temperature thermal management application. The encapsulation ratio of PEG is controlled by controlling the core flow rate, and ~ 93% heat energy storage efficacy is apparent for 1.5 mlh−1 of core flow rate. Moreover, the prepared fiber possesses maximum latent melting and freezing enthalpy of 30.1 ± 3.7 and 25.6 ± 4.0 Jg−1, respectively. The transient dynamic temperature vs. time curve of the rGO-loaded phase change fiber demonstrates the delay of fiber surface temperature change compared to pristine fiber. We indeed show that the tunable heat transfer and thermal energy storage efficacy of phase change fiber is achieved via controlled liquid PEG delivery and the addition of rGO in shell architecture. Notably, the effectiveness of unique phase change material (PCM)–based core–shell fibers is concluded from advanced scanning thermal microscopy (SThM) and self-thermoregulation tests.
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