One-step generation of hollow graphitic carbon nanospheres with suitable oxygenated structures as conductive additives for water-soluble binder in highly stable supercapacitor electrodes

Abstract

Although the weight ratio of electron conductive additives and the binder to porous carbons in the electrode component of electric double-layer capacitors (EDLC) is minimal, however, without them the electrochemical performances of EDLC would decay quickly. In this work, we present a one-step approach for manufacturing a unique conductive carbon material that shows highly connecting hollow structures as well as approximate oxygenated surface groups to create a synergy effect with aqueous binder and the main component, porous carbon. The as-prepared carbon nanospheres (HCNs) were generated from a typical carbon black-PC20 in air (denoted as PC20HT) at mild temperatures ranging from 400 to 700 °C for 2–4 h at a massive scale of approximate 1 kg h−1. The as-prepared PC20HT displays a high specific surface area of 657 m2 g−1 (the pristine PC20 has 112 m2 g−1) with a pore volume of 0.71 cm3 g−1, and an oxygen content of 14.10 wt%. Interestingly, a premixing of PC20HT and porous carbon is required before making the electrode pastes. The well-premixed carbon materials and a water-soluble binder-polyacrylic acid are composed into highly-stable components as EDLC electrodes in an organic electrolyte. As consequently, the PC20HT-assisted electrodes demonstrate highly stable life cycles (charge-discharge behaviors), with a retention rate 82.13 % over 50,000 cycles at a narrow voltage window of 2.5–2.7 V at 0.5 A g−1 when compared to two conventional conductive carbons, BP2000 (68.45 %) and Super P (67.46 %). Thermal annealing at 900 °C in Ar reduces the oxygen content of PC20HT to 4.25 wt% (referred to as TPC20HT), increasing the retention rate of life cycle to 88.89 % after the same cycles. TPC20HT-assisted EDLC electrodes exhibit a superior energy density of 34.76 Wh kg−1, which is higher than CB-BP2000 and Super P-assisted EDLC electrodes. The transforming of structural morphologies as well as the surface oxygenated and graphitic structures of the as-prepared HCS, PC20HT, and TPC20HT were also described before and after long-term cycling. This simple route for producing conductive carbons is applicable in an aqueous binder system for preparing EDLC electrodes with a cost-effective and environmentally friendly approach.