Multiscale Structural Modulation of Anisotropic Graphene Framework for Polymer Composites Achieving Highly Efficient Thermal Energy Management

Graphene is usually embedded into polymer matrices for the development of thermally conductive composites, preferably forming an interconnected and anisotropic framework. Currently, the directional self‐assembly of exfoliated graphene sheets is demonstrated to be the most effective way to synthesize anisotropic graphene frameworks. However, achieving a thermal conductivity enhancement (TCE) over 1500% with per 1 vol% graphene content in polymer matrices remains challenging, due to the high junction thermal resistance between the adjacent graphene sheets within the self‐assembled graphene framework. Here, a multiscale structural modulation strategy for obtaining highly ordered structure of graphene framework and simultaneously reducing the junction thermal resistance is demonstrated. The resultant anisotropic framework contributes to the polymer composites with a record‐high thermal conductivity of 56.8–62.4 W m−1 K−1 at the graphene loading of ≈13.3 vol%, giving an ultrahigh TCE per 1 vol% graphene over 2400%. Furthermore, thermal energy management applications of the composites as phase change materials for solar‐thermal energy conversion and as thermal interface materials for electronic device cooling are demonstrated. The finding provides valuable guidance for designing high‐performance thermally conductive composites and raises their possibility for practical use in thermal energy storage and thermal management of electronics. The dual‐assembled graphene framework (DAGF), which combines a highly oriented graphene structure along the vertical direction and a low junction thermal resistance between the graphene building blocks, exhibits excellent performance in improving the thermal conductivity of polymers. The resultant composites have a record‐high thermal conductivity of 56.8–62.4 W m−1 K−1(≈13.3 vol%), significantly outperforming previously reported results.