Transparent conducting oxide-free nitrogen-doped graphene/reduced hydroxylated carbon nanotube composite paper as flexible counter electrodes for dye-sensitized solar cells

Three-dimensional nitrogen-doped graphene/reduced hydroxylated carbon nanotube composite aerogel (NG/CNT-OH) with unique hierarchical porosity and mechanical stability is developed through a two-step hydrothermal reaction. With plenty of exposed active sites and efficient multidimensional transport pathways of electrons and ions, NG/CNT-OH exhibits great electrocatalytic performances for I⁻/I₃⁻ redox couple. The subsequent compressed NG/CNT-OH papers possess high electrical conductivity and good flexibility, thus generating high-performance flexible counter electrodes (CEs) with transparent conducting oxide free (TCO-free) for dye-sensitized solar cells (DSSCs). The flexible NG/CNT-OH electrodes show good stability and the DSSCs with the optimized NG/CNT-OH CE had higher short-circuit current density (13.62 mA cm⁻²) and cell efficiency (6.36%) than DSSCs using Pt CE, whereas those of the DSSCs using Pt CE were only 12.81 mA cm⁻² and 5.74%, respectively. Increasing the ratio of hydroxylated carbon nanotubes (CNT-OH) to the graphene oxide (GO) in the reactant would lead to less content of doped N, but better diffusion of electrolyte in the CEs because of more complete GO etching reaction. The design strategy presents a facile and cost effective way to synthesis three-dimensional graphene/CNT composite aerogel with excellent performance, and it can be potentially used as flexible TCO-free CE in other power conversion or energy storage devices.