Tunable Negative Permittivity in Graphene/Poly(Vinylidene Fluoride) Composites with Low Percolation Threshold

Recently, metamaterials with fascinating dielectric behavior have drawn much attention for their potential applications. Herein, percolating graphene/poly(vinylidene fluoride) (GR/PVDF) composites consisting of GR sheets homogeneously dispersed in PVDF matrix are fabricated via hot‐pressing method in 20 Hz–1 MHz frequency regions, of which simultaneously realizing negative permittivity with low percolation threshold. It is demonstrated that the negative permittivity of GR/PVDF composites is resulted from the low‐frequency plasma oscillation of free electrons, and a universal regulatory mechanism of the Drude model is analyzed. At the same time, rapid formative 3D GR conductive networks contributed to the low percolation threshold (7.78 wt%) of composites. Moreover, it is shown that electrical percolation occurs in samples as GR content exceeds percolation threshold, indicating a typical metal‐like behavior. In addition, the reactance is discussed according to the equivalent circuit analysis. This work constructed the metacomposites with low filler content, which is a benefit for practical applications in electromagnetic devices.