Facile preparation of polybenzoxazine-based carbon microspheres with nitrogen functionalities: effects of mixed solvents on pore structure and supercapacitive performance

Abstract

In this study, polybenzoxazine (PBZ)-based carbon microspheres were prepared via a facile method using a mixture of formaldehyde (F) and dimethylformamide (DMF) as the solvent. The PBZ microspheres were successfully obtained at the F/DMF weight ratios of 0.4 and 0.6. These microspheres exhibited high nitrogen contents after carbonization. The microstructures of all the samples showed an amorphous phase and a partial graphitic phase. The porous carbon with the F/DMF ratio of 0.4 showed significantly higher specific capacitance (275.1 F∙g^‒1) than the reference carbon (198.9 F∙g^‒1) at 0.05 A∙g^‒1. This can be attributed to the synergistic electrical double-layer capacitor and pseudo-capacitor behaviors of the porous carbon with the F/DMF ratio of 0.4. The presence of nitrogen/oxygen functionalities induced pseudo-capacitance in the microspheres, and hence increased their total specific capacitance. After activation with CO₂, the specific surface area of the carbon microspheres with the F/DMF ratio of 0.4 increased from 349 to 859 m²∙g^‒1 and the specific capacitance increased to 424.7 F∙g^‒1. This value is approximately two times higher than that of the reference carbon. The results indicated that the F/DMF ratio of 0.4 was suitable for preparing carbon microspheres with good supercapacitive performance. The nitrogen/oxygen functionalities and high specific surface area of the microspheres were responsible for their high capacitance.

Key words： PBZ; carbon; porous materials; microsphere; supercapacitor

Acknowledgments

This work was financially supported by Walailak University (Grants No. WU60103) and the Thailand Research Fund and Office of the Higher Education Commission (MRG6180042). The authors express their heart-felt thanks to the Thailand Research Fund (Senior Research Scholar) and the Energy Conservation Promotion Fund, Energy Policy and Planning Office, Ministry of Energy, Thailand for the financial support. This research was partially supported by the New Strategic Research (P2P) project, Walailak University, Thailand. This work was supported by Walailak University Fund. Special thanks to Assoc. Prof. Pannipa Chaowana and Mr. Nopparat Sangtong for their valuable suggestions.

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