Achieving Metal‐Level Thermal Conductivity in Multifunctional Graphene‐based Composites via Coordination‐Driven Vacuum‐Assisted Layer‐by‐Layer Self‐Assembly Process

ABSTRACT Graphene, endowed with ultra‐high thermal conductivity, has always been the top candidate for developing high‐performance heat management materials. The challenges in acquiring high‐quality graphene and in tailoring of fabrication processes for graphene‐based heat dissipation materials hinder their widespread application. Inspired by the coordination effects observed in biomaterials, multifunctional thermal management composites were fabricated from edge‐oxidized graphene (EGO) via a coordination bond‐facilitated layer‐by‐layer self‐assembly process. Benefiting from the preserved essential structure of graphene due to selective oxidation and the oriented heat transport pathways driven by coordination bonds, Fe 3+ ‐coordinated EGO film (EGO‐(Fe 3+ ) 2 ‐F) boasted a metal‐like in‐plane thermal conductivity of 147.2 W m −1 K −1 . DFT and MD simulations were employed to probe the role of coordination bonds‐enabled interfacial electron transfer in optimizing the electron‐phonon coupling mediated heat transfer in the EGO‐(Fe 3+ ) 2 ‐F. Leveraging the magnetic properties and the octahedral interfacial structure between EGO conferred by Fe 3+ ‐mediated coordination bonds, the EGO‐(Fe 3+ ) 2 ‐F achieved an EMI SE of over 80 dB in Ka‐band, alongside a substantial tensile strength of 43 MPa. Excellent Joule heating and heat‐stimuli responsiveness of EGO‐(Fe 3+ ) 2 ‐F validated the attainment of high‐quality graphene. Our work offers a unique pathway to realize the application potential of graphene in the thermal management of electronic devices.