Microsupercapacitors (MSCs) have drawn great attention for use as miniaturized electrochemical energy storage devices in portable, wearable, as well as implantable electronics. Many materials have been developed as electrodes for MSCs. However, the thin-film fabrication for most of these materials involves multistep operations, including filtration, spray coating, and sputtering. Most importantly, these methods present challenges for the preparation of thin films at the atomic or molecular scale. Therefore, the understanding of performance of ultrathin-film-based MSCs remains challenge. Herein, a B/N-enriched polymer film is successfully prepared using the photoassisted interfacial approach. The as-synthesized polymer film exhibits typical semiconductive characteristics and can be easily scaled up to a large area of up to tens of square centimeters. This ultrathin polymer film can be directly transferred to silicon wafers to fabricate MSC through laser scribing. The prepared MSC exhibits specific volumetric capacitance as high as 20.9 F cm −3 , corresponding to volumetric energy density of 2.9 mWh cm −3 (at 0.1 V s −1 ). Moreover, the volumetric power density can reach 1461 W cm −3 , surpassing most existing semiconductive polymer film-based MSC devices. In addition, the prepared MSC exhibits typical AC line-filtering ability (−67°at 120 Hz). This study offers a facile interfacial approach to preparing semiconductive polymer films with aromatic moieties for microsized energy storage devices.

Cobalt-doped graphene-coupled hypercrosslinked polymers (Co-GHCP) have been successfully prepared on a large scale, using an efficient RAFT (Reversible Addition-Fragmentation Chain Transfer Polymerization) emulsion polymerization and nucleophilic substitution reaction with Co (II) porphyrin. The Co-GHCP could be transformed into cobalt-doped porous carbon nanosheets (Co-GPC) through direct pyrolysis treatment. Such a Co-GPC possesses a typical 2D morphology with a high specific surface area of 257.8 m2 g−1. These intriguing properties of transition metal-doping, high conductivity, and porous structure endow the Co-GPC with great potential applications in energy storage and conversion. Utilized as an electrode material in a supercapacitor, the Co-GPC exhibited a high electrochemical capacitance of 455 F g−1 at a specific current of 0.5 A g−1. After 2000 charge/discharge cycles, at a current density of 1 A g−1, the specific capacitance increased by almost 6.45%, indicating the excellent capacitance and durability of Co-GPC. These results demonstrated that incorporation of metal porphyrin into the framework of a hypercrosslinked polymer is a facile strategy to prepare transition metal-doped porous carbon for energy storage applications.