This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0% has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM 1.5G, 100 mW/cm2). Such high efficiency can even rival that of its counterpart DSC using a state-of-the-art iodine-based electrolyte in the systems studied.The cation effects of lithium, sodium and guanidinium ions in liquid electrolytes for DSCs have been scrutinized. The selection of the type of cations has been found to exert quite different impacts on the conduction band edge (CB) of the TiO2 and also on the electron recombination kinetics, therefore resulting in different photovoltaic behavior. / QC 20120124

The long-term outdoor durability of dye-sensitized solar cells (DSSCs) is still a challenging issue for the large-scale commercial application of this promising photovoltaic technique. In order to study the degradation mechanism of DSSCs, ageing tests under selected accelerating conditions were carried out. The electrolyte is a crucial component of the device. The interactions between the electrolyte and other device components were unraveled during the ageing test, and this is the focus of this thesis. The dynamics and the underlying effects of these interactions on the DSSC performance were studied. Co(bpy)32+/3+-mediated solar cells sensitized by triphenylamine-based organic dyes are systems of main interest. The changes with respect to the configuration of both labile Co(bpy)32+ and apparently inert Co(bpy)33+ redox complexes under different ageing conditions have been characterized, emphasizing the ligand exchange problem due to the addition of Lewis-base-type electrolyte additives and the unavoidable presence of oxygen. Both beneficial and adverse effects on the DSSC performance have been separately discussed in the short-term and long-term ageing tests. The stability of dye molecules adsorbed on the TiO2 surface and dissolved in the electrolyte has been studied by monitoring the spectral change of the dye, revealing the crucial effect of cation-based additives and the cation-dependent stability of the device photovoltage. The dye/TiO2 interfacial electron transfer kinetics were compared for the bithiophene-linked dyes before and after ageing in the presence of Lewis base additives; the observed change being related to the light-promoted and Lewis-base-assisted performance enhancement. The effect of electrolyte co-additives on passivating the counter electrode was also observed. The final chapter shows the effect of electrolyte composition on the electrolyte diffusion limitation from the perspectives of cation additive options, cation concentration and solvent additives respectively. Based on a comprehensive analysis, suggestions have been made regarding lithium-ion-free and polymer-in-salt strategies, and also regarding cobalt complex degradation and the crucial role of Lewis base additives. The fundamental studies contribute to the understanding of DSSC chemistry and provide a guideline towards achieving efficient and stable DSSCs. / <p>QC 20160517</p>