Sustainable Upcycling of Nitrogen-Enriched Polybenzoxazine Thermosets into Nitrogen-Doped Carbon Materials for Contriving High-Performance Supercapacitors

Abstract

Nitrogen-enriched polybenzoxazine thermosets derived from the ring-opening polymerization of side-chain-type benzoxazine-functionalized polyethylenimine resins (Bz-pei) have been previously reported by our group. In view of the appreciable nitrogen content and significant char yield, these thermosets have been envisioned as enticing carbon precursors and therefore have been sustainably upcycled to nitrogen-doped carbon materials. It is worth mentioning that the sustainable upcycling method should circumscribe energy as well as cost consumption, due to which carbon materials in the present work have been developed under moderate carbonization conditions, without chemical activation treatment. The developed nitrogen-doped carbon materials have been characterized by using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, elemental analysis, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The pore topography has been analyzed using scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) analysis has been performed, while the Brunauer–Emmett–Teller (BET) surface area has been determined using nitrogen adsorption–desorption experiments. A comparison of the results obtained from electrochemical investigations performed in a three-electrode setup shows that carbon material upcycled from the guaiacol-based polybenzoxazine thermoset, exhibiting 6.4% nitrogen doping in the carbon framework (labeled as C-GP81), exhibits an impressive capacitance of 700 F g–1 at 10 A g–1 current density, suggesting excellent efficiency and rate capability of the obtained N-doped carbon-material-based supercapacitor electrodes. Furthermore, the carbon material designated as C-GP81 could deliver a maximum energy density (E d) of 48 Wh kg–1 at a power density (P d) of 8400 W kg–1 in a three-electrode configuration. The performance of the crafted supercapacitor device for the present study has surpassed the performance reported for polybenzoxazine-derived carbons. Additionally, the performance of carbon material labeled as C-GP81 has been evaluated for its potential as an active component in the electrodes of a symmetric device.

Mini-Review on Organic Electrode Materials: Recent Breakthroughs and Advancement in Metal Ion Batteries

“…Pratibha et al reported a nitrogen-enriched guaiacol-based polybenzoxazine thermoset with 6.4% nitrogen doping in the carbon framework, which exhibited an amazing capacitance of 700 F g −1 at a current density of 10 A g −1 , indicating excellent efficiency and rate capability of the obtained nitrogen-doped carbon-materialbased supercapacitor electrodes. 73 5.4. Nonconjugated Polymers.…”

“…The nitrogen-doped carbon materials obtained from the upcycling of nitrogen-enriched polybenzoxazine thermosets have been characterized and evaluated for their potential as active components for supercapacitor electrodes as they exhibited enhanced electronic conduction. Pratibha et al reported a nitrogen-enriched guaiacol-based polybenzoxazine thermoset with 6.4% nitrogen doping in the carbon framework, which exhibited an amazing capacitance of 700 F g –1 at a current density of 10 A g –1 , indicating excellent efficiency and rate capability of the obtained nitrogen-doped carbon-material-based supercapacitor electrodes …”

In Situ Self-Assembly of Nitrogen-Doped 3D Flower-like Hierarchical Porous Carbon and Its Application for Supercapacitors

“…However, the expensive template, toxic (corrosive) reagent, as well as catalyst, is exploited during (after) the carbonization [ 28 , 30 , 31 ]. Additionally, introducing rich heteroatom doping could render a further improvement to the electrochemical properties of carbon-based electrodes [ 32 ]. Hence, it is essential to develop a simple and effective approach for harvesting useful carbon materials.…”

Preparation and Characterization of Carbon Aerogel Based on Main-Chain Benzoxazine

“…Polybenzoxazine (PBZ), as a resin with good thermal performance, is considered promising candidates for the role of porous carbon aerogel . Structurally, PBZ is made up of a cross-linked network of Mannich and phenolic linkages, which is derived from the thermally accelerated ring-opening polymerization of benzoxazine monomers, without using a catalyst . PBZ molecules can be prepared from a variety of available and inexpensive primary amines, phenols, and formaldehyde, so the structure of the precursor made from PBZ can be adjusted to the surface chemistry required by the porous carbon aerogel. , The high molecular design flexibility allows for a variety of molecular structures of desired properties .…”