Conductive polymer composites (CPCs) have generated significant academic and industrial interest for several decades. Unfortunately, ordinary CPCs with random conductive networks generally require high conductive filler loadings at the insulator/conductor transition, requiring complex processing and exhibiting inferior mechanical properties and low economic affordability. Segregated CPC (s-CPC) contains conductive fillers that are segregated in the perimeters of the polymeric granules instead of being randomly distributed throughout the bulk CPC material; these materials are overwhelmingly superior compared to normal CPCs. For example, the s-CPC materials have an ultralow percolation concentration (0.005–0.1 vol%), superior electrical conductivity (up to 106 S/m), and reasonable electromagnetic interference (EMI) shielding effectiveness (above 20 dB) at low filler loadings. Therefore, considerable progress has been achieved with s-CPCs, including high-performance anti-static, EMI shielding and sensing materials. Currently, however, few systematic reviews summarizing these advances with s-CPCs are available. To understand and efficiently harness the abilities of s-CPCs, we attempted to review the major advances available in the literature. This review begins with a concise and general background on the morphology and fabrication methods of s-CPCs. Next, we investigate the ultralow percolation behaviors of and the elements exerting a relevant influence (e.g., conductive filler type, host polymers, dispersion methods, etc.) on s-CPCs. Moreover, we also briefly discussed the latest advances in the mechanical, sensing, thermoelectric and EMI shielding properties of the s-CPCs. Finally, an overview of the current challenges and tasks of s-CPC materials is provided to guide the future development of these promising materials.
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