Chemically Edge-Carboxylated Graphene Enhances the Thermal Conductivity of Polyetherimide–Graphene Nanocomposites

In this work, we demonstrate that edge oxidation of graphene can enable larger enhancement in thermal conductivity (k) of graphene nanoplatelet (GnP)/polyetherimide (PEI) composites relative to oxidation of the basal plane of graphene. Edge oxidation offers the advantage of leaving the basal plane of graphene intact, preserving its high in-plane thermal conductivity (kin > 2000 W m–1 K–1), while, simultaneously, the oxygen groups introduced on the graphene edge enhance interfacial thermal conductance through hydrogen bonding with oxygen groups of PEI, enhancing the overall polymer composite thermal conductivity. Edge oxidation is achieved in this work by oxidizing graphene in the presence of sodium chlorate and hydrogen peroxide, thereby introducing an excess of carboxyl groups on the edge of graphene. Basal plane oxidation of graphene, on the other hand, is achieved through the Hummers method, which distorts the sp2 carbon–carbon network of graphene, dramatically lowering its intrinsic thermal conductivity, causing the BGO/PEI (BGO = basal-plane oxidized graphene or basal-plane-functionalized graphene oxide) composite’s k value to be even lower than pristine GnP/PEI composite’s k value. The resulting thermal conductivity of the EGO/PEI (EGO = edge-oxidized graphene or edge-functionalized graphene oxide) composite is found to be enhanced by 18%, whereas that of the BGO/PEI composite is diminished by 57%, with respect to the pristine GnP/PEI composite with 10 wt % GnP content. Two-dimensional Raman mapping of GnPs is used to confirm and distinguish the location of oxygen functional groups on graphene. The superior effect of edge bonding presented in this work can lead to fundamentally novel pathways for achieving high thermal conductivity polymer composites.