Electrocatalytic Zinc Composites as the Efficient Counter Electrodes of Dye-Sensitized Solar Cells: Study on the Electrochemical Performances and Density Functional Theory Calculations

Highly efficient zinc compounds (Zn₃N₂, ZnO, ZnS, and ZnSe) have been investigated as low-cost electrocatalysts for the counter electrodes (CE) of dye-sensitized solar cells (DSSCs). Among them, Zn₃N₂ and ZnSe are introduced for the first time in DSSCs. The zinc compounds were separately mixed with a conducting binder, poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and thereby four composite films of Zn₃N₂/PEDOT:PSS, ZnO/PEDOT:PSS, ZnS/PEDOT:PSS, and ZnSe/PEDOT:PSS were coated on the tin-doped indium oxide (ITO) substrates through a simple drop-coating process. In the composite film, nanoparticles of the zinc compound form active sites for the electrocatalytic reduction of triiodide ions, and PEDOT:PSS provides a continuous conductive matrix for fast electron transfer. By varying the weight percentage (5-20 wt %) of a zinc compound with respect to the weight of the PEDOT:PSS, the optimized concentration of a zinc compound was found to be 10 wt % in all four cases, based on the photovoltaic performances of the corresponding DSSCs. At this concentration (10 wt %), the composites films with Zn₃N₂ (Zn₃N₂-10), ZnO (ZnO-10), ZnS (ZnS-10), and ZnSe (ZnSe-10) rendered, for their DSSCs, power conversion efficiencies () of 8.73%, 7.54%, 7.40%, and 8.13%, respectively. The difference in the power conversion efficiency is explained based on the electrocatalytic abilities of those composite films as determined by cyclic voltammetry (CV), Tafel polarization plots, and electrochemical impedance spectroscopy (EIS) techniques. The energy band gaps of the zinc compounds, obtained by density functional theory (DFT) calculations, were used to explain the electrocatalytic behaviors of the compounds. Among all the zinc-based composites, the one with Zn₃N₂-10 showed the best electrocatalytic ability and thereby rendered for its DSSC the highest of 8.73%, which is even higher than that of the cell with the traditional Pt CE (8.50%). Therefore, Zn₃N₂ can be considered as a promising inexpensive electrocatalyst to replace the rare and expensive Pt.