An Effective Strategy to Achieve Ultralow Electrical Percolation Threshold with CNTs Anchoring at the Interface of PVDF/PS Bi‐Continuous Structures to Form an Interfacial Conductive Layer

Abstract Conductive composites based on polymers and conductive nanofillers are widely studied as a promising material. The rational design of 3D conductive networks in composites is crucial to improve their electrical conductivity and reduce the dosage of nanofillers. Herein, poly(vinylidene fluoride) (PVDF) and polystyrene (PS) bi‐continuous structures with modified carbon nanotubes (CNTs) tailored to anchor at the interface are designed to achieve an ultralow electrical percolation threshold because of the formation of a thin interfacial conductive layer. In this work, the modification of CNTs with poly(methyl methacrylate) (PMMA), which contributes to the improvement of the compatibility between PVDF and CNTs, is effective to control the distribution of CNTs in composites. It promotes the migration of CNTs from the PS phase to the interface of PVDF and PS. Consequently, the interfacial conductive layer is formed at a low CNT content, and the electrical percolation threshold of PVDF/PS/CNTs‐PMMA nanocomposites is only 0.07 vol%, having a great decrease of about 50% compared with that of PVDF/PS/CNTs nanocomposites. Thus, it is demonstrated that the distribution of CNTs can be tailored to anchor at the interface by proper chemical modification to form an interfacial conductive layer and a decrease of percolation threshold can also be achieved.