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

doi:10.1007/s11705-019-1899-8

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (6) : 1072-1086 https://doi.org/10.1007/s11705-019-1899-8

RESEARCH ARTICLE

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

Uthen Thubsuang¹(

), Suphawadee Chotirut¹, Apisit Thongnok¹, Archw Promraksa¹, Mudtorlep Nisoa², Nicharat Manmuanpom^3,⁴, Sujitra Wongkasemjit^3,⁴, Thanyalak Chaisuwan^3,⁴

¹. School of Engineering and Technology, Walailak University, Nakhon Si Thammarat 80160, Thailand
². School of Science, Walailak University, Nakhon Si Thammarat 80160, Thailand
³. The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand
⁴. Center of Excellence on Petrochemical and Materials Technology, Bangkok 10330, Thailand

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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.

Keywords PBZ carbon porous materials microsphere supercapacitor

Corresponding Author(s): Uthen Thubsuang

Just Accepted Date: 30 December 2019 Online First Date: 24 February 2020 Issue Date: 11 September 2020

Cite this article:

Uthen Thubsuang,Suphawadee Chotirut,Apisit Thongnok, et al. Facile preparation of polybenzoxazine-based carbon microspheres with nitrogen functionalities: effects of mixed solvents on pore structure and supercapacitive performance[J]. Front. Chem. Sci. Eng., 2020, 14(6): 1072-1086.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1899-8
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I6/1072

Fig.1 Scheme 1 Synthesis of carbon microspheres.

Fig.2 (a) FTIR spectra, (b) feasible structures, (c) DSC thermograms, and (d) TGA thermograms of MCBP and PBZ.

Fig.3 (a–e) FE-SEM images of the samples (inset: graphical model for the observed particles); (f) TEM image of AC-0.4.

Fig.4 Particle size distributions of (a) C-0.2, (b) C-0.4, (c) C-0.6, and (d) AC-0.4.

Fig.5 (a) XRD patterns and (b) Raman spectra of the as-prepared porous carbons.

Fig.6 Nitrogen adsorption-desorption isotherms for (a) C-Ref, (b) C-0.2, (c) C-0.4, (d) C-0.6, and (e) AC-0.4 and the (f) pore size distributions of all the samples.

Tab.1 Pore structure of the samples

Fig.7 Pore size distributions of C-Ref, C-0.2, C-0.4, and C-0.6.

Fig.8 (a) XPS N1s spectra of all the samples, (b) pseudo-Faradaic reaction of N-5 and N-6 [⁷,¹²], (c) XPS O1s spectra of all the samples, and (d) pseudo-Faradaic reaction of O-1 [¹²].

Tab.2 Elemental compositions of all the samples

Fig.9 (a) CV profiles of all the samples at 1 mV?s^?¹, (b) CV profile of C-0.4 at various scan rates, (c) GCD curves of all the samples at 0.1 A?g^?¹, (d) GCD curves of AC-0.4 at various current densities, (e) specific capacitance of all the samples as a function of the current density, and (f) Ragone plots for all the samples.

Fig.10 Laboratory-scale supercapacitor illuminating a red LED.

Fig.11 Nyquist plots for all the samples (a) large scale and (b) enlarged scale in the high-frequency region.

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