Thermally conductive polymer nanocomposites are enticing candidates for not only thermal managements in electronics but also functional components in emerging thermal energy storage and conversion systems and intelligent devices. A high thermal conductivity (k) depends largely on the ordered assembly of high-k fillers in the composites. In the past decades, various templating assembly techniques have been developed to rationally construct nanoscale fillers into three-dimensional (3D) interconnected structures, further improving the k of composites compared to conventional methods. Herein, recent advances are summarized in developing thermally conductive polymer composites based on self-templating, sacrificial templating, foam-templating, ice-templating and template-directed chemical vapor deposition techniques. These unique templating methods to fabricate 3D interconnected fillers in the form of segregated, cellular, lamellar, and radially aligned structures are reviewed, and their correlations to the k of composites are thoroughly probed. Moreover, multiscale structural design strategies combined with different templating methods to further improve the k of composites are highlighted. This review offers a constructive guidance to fabricate next-generation thermally conductive polymer composites for diverse thermal energy applications.

导热聚合物纳米复合材料不仅是电子产品热管理的诱人候选者，而且还是新兴热能存储和转换系统以及智能设备中功能组件的诱人候选者。高导热率 ( k ) 在很大程度上取决于复合材料中高k填料的有序组装。在过去的几十年中，已经开发出各种模板组装技术来合理地将纳米级填料构造成三维 (3D) 互连结构，进一步提高了k与传统方法相比的复合材料。在此，总结了基于自模板、牺牲模板、泡沫模板、冰模板和模板导向化学气相沉积技术开发导热聚合物复合材料的最新进展。回顾了这些以分离、蜂窝、层状和径向排列结构形式制造 3D 互连填料的独特模板方法，并彻底探讨了它们与复合材料k的相关性。此外，多尺度结构设计策略结合不同的模板方法进一步提高了k突出显示了复合材料。这篇综述为制造用于各种热能应用的下一代导热聚合物复合材料提供了建设性的指导。