Graphene quantum dot-decorated carbon electrodes for energy storage in vanadium redox flow batteries

Abstract

Nitrogen-doped graphene quantum dots (GQDs) and graphitic carbon nitride (g-C₃N₄) quantum dots are synthesized via a solid-phase microwave-assisted (SPMA) technique. The resulting GQDs are deposited on graphite felt (GF) and are employed as high-performance electrodes for all-vanadium redox flow batteries (VRFBs). The SPMA method is capable of synthesizing highly oxidized and amidized GQDs using citric acid and urea as the precursor. The as-prepared GQDs contain an ultrahigh O/C (56–61%) and N/C (34–66%) atomic ratio, much higher than the values reported for other carbon-based nano-materials (e.g. oxidized activated carbon, carbon nanotubes, and graphene oxide). Three types of quantum dots, having an average particle size of 2.8–4.2 nm, are homogeneously dispersed onto GF electrodes, forming GQD/GF composite electrodes. Through deposition of GQDs onto the electrode structure, the catalytic activity, equivalent series resistance, durability, and voltage efficiency are improved. The capacity utilization using GQD/GF electrode is substantially enhanced (∼69% increase within 40 cycles). The improved performance is attributed to the synergistic effect of GQDs containing oxygen functionalities (epoxy, phenolic and carboxylic groups) and lattice N atoms (quaternary, pyrrolic and pyridinic N) which result in enhanced wettability and increased electrochemical surface area providing increased reaction sites.