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Frontiers of Chemical Science and Engineering

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 Manmuanpom3,4, Sujitra Wongkasemjit3,4, Thanyalak Chaisuwan3,4
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 Fg‒1) than the reference carbon (198.9 Fg‒1) at 0.05 Ag‒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 m2g‒1 and the specific capacitance increased to 424.7 Fg‒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.
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http://journal.hep.com.cn/fcse/EN/10.1007/s11705-019-1899-8
http://journal.hep.com.cn/fcse/EN/Y2020/V14/I6/1072
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Uthen Thubsuang
Suphawadee Chotirut
Apisit Thongnok
Archw Promraksa
Mudtorlep Nisoa
Nicharat Manmuanpom
Sujitra Wongkasemjit
Thanyalak Chaisuwan
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.
Sample SBETa) /(m2?g-1) Vmicrob) /(cm3?g-1) Vmesoc) /(cm3?g-1) VTd) /(cm3?g-1) APSe) /nm
C-Ref 336 0.17 0.02 0.19 1.0
C-0.2 331 0.13 0.07 0.20 1.2
C-0.4 349 0.14 0.06 0.20 1.2
C-0.6 310 0.11 0.07 0.18 1.2
AC-0.4 859 0.43 0.02 0.45 1.0
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].
Sample XPS/wt-% Elemental analyzer/%
C N O C H N Other elements
C-Ref 84.8 3.4 11.8 78.6 1.8 4.2 15.4
C-0.2 88.3 4.7 7.0 77.2 1.7 5.0 16.1
C-0.4 85.3 5.0 9.7 79.5 1.7 5.4 13.4
C-0.6 79.9 5.7 14.4 79.2 1.7 5.3 13.8
AC-0.4 89.3 4.2 6.5 75.4 2.0 4.3 18.3
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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