Anomalous size effects of ultra-small graphene sheets on the thermal properties of macroscopic films

Graphene films assembled from graphene nanosheets have achieved a wide range of applications in thermal management due to their ultra-high thermal conductivity. Although it is well established in the micron range that increasing the lateral size of graphene sheets enhances the thermal conductivity of graphene films. However, the preparation of large-size graphene sheets and their assembly into ordered film structures remain challenging, which impedes the development of high-performance thermally conductive graphene films. Herein, by unifying the properties of graphene sheets and preparation processes, we correlate the thermal conductivity of graphene films and the lateral size of starting sheets ranging from 0.32 to 20.32 μm and probe the underlying mechanism from the perspectives of macroscopic and microscopic structural defects. Surprisingly, decreasing lateral size to 0.32 μm achieved as high in-plane thermal conductivity (K//, 1550.06 ± 12.99 W/mK) and significantly higher through-plane thermal conductivity (K⊥, 8.11 ± 0.08 W/mK) of graphene films as the case of 20.32 μm. Besides, the commonly overlooked size effect of K⊥ shows an unexpected negative correlation, and the size effect of K// is also not monotonically increasing. These phenomena are correlated with micro-structure defects and lattice defects. Mechanism analysis reveals that thermally induced gas generation and the complex gas-sheet interactions during micro-structure evolution play a critical role in the size effect and may explain the unexpected negative size effect in the sub-micro range. These findings in size effects provide theoretical guidance for the selection of raw materials in fabricating highly thermally conductive graphene films.