Kinetics of Charge Transfer at Carbon-Based Counter Electrodes for Dye-Sensitized Solar Cells with Aqueous Electrolytes

Abstract

Dye-sensitized solar cells (DSSCs) might provide a highly sustainable alternative for next generation photovoltaics. This is due to their low-energy production from abundant materials, short energy payback time, high efficiency under low illumination intensities (i.e., diffuse light or indoor conditions), and versatile concepts of applications. However, some commonly used electrolyte components are environmentally problematic. Acetonitrile or other volatile organic solvents, e.g., as well as carcinogenic cobalt complexes should not leak from DSSCs. Sealing foils, however, which are typically used to prevent such leakage, carry a risk of long-term failure.Replacing the organic solvent by water offers several advantages, as it is environmentally benign, less volatile and the cell function, further, cannot be damaged by the intrusion of water vapor. Instead of Co-complexes, e.g., the stable organic radical TEMPO (2,2,6,6-tretramethylpiperidine-1-oxyl) can serve as an alternative redox mediator with a highly positive redox potential (0.71 V vs. NHE). Using TEMPO, power conversion efficiencies (PCE) of up to 4.3% and high open-circuit voltages (V oc = 0.955 V) have been reported.[1] However, the use of TEMPO is limited by its solubility in water (C max < 0.15 M). Its derivative 4-hydroxy-TEMPO (OH-TEMPO) possesses a significantly higher solubility in water (C max > 2 M) and a more positive redox potential (0.81 V vs. NHE), making it a promising candidate as a redox mediator.In this work, we built DSSCs with TEMPO and OH-TEMPO based aqueous electrolytes, Y123-sensitized TiO2 photoanodes, and counter electrodes coated with poly(3,4-ethylenedioxythiphene) (PEDOT). For OH-TEMPO, the short-circuit current density (j sc) and open-circuit voltage were higher than with TEMPO, but the fill factor (FF) and the PCE were significantly lower. By impedance studies, large charge transfer resistances at the counter electrode (R CE) were obtained for OH-TEMPO in combination with additives such as 1-methylbenzimidazole (MBI), indicating a strong kinetic limitation of the OH-TEMPO+ reduction. However, we found that such additives as MBI or other organic compounds, are necessary to suppress recombination at the photoanode/electrolyte interface. Thus, we subsequently studied different counter electrode materials, such as platinum (reference), conducting polymers, and carbon materials, in contact to OH-TEMPO electrolytes with MBI to determine R CE and find suitable materials for the application in DSSCs.[1] Yang, W., Söderberg, M., Eriksson, A. I. K. & Boschloo, G. Efficient aqueous dye-sensitized solar cell electrolytes based on a TEMPO/TEMPO+ redox couple. RSC Advances 5, 26706–26709 (2015).