Over the last decades, iodine-free redox couples have been widely investigated as alternatives for the ubiquitous triiodide/iodide redox shuttle in dye-sensitized solar cells (DSCs). This is mainly motivated by desires to overcome the disadvantages associated with the latter, such as large energy loss in the dye regeneration process, visible light absorption and corrosiveness towards current-collecting metal grids. However, conventional Pt cathodes show poor catalytic activity towards those iodine-free redox couples, resulting in poor fill factors and relatively moderate power conversion efficiencies. The ultimate solution to address this challenge is to develop alternative economical Pt-free catalysts. This review selectively discusses and summarizes the recent advances in novel cathode materials for electrolytes free of iodine-based redox couples, mainly including inorganic transition metal compounds, organic conductive polymers and carbonaceous materials (particularly carbon nanotubes and graphene). Most of these advances have been realized by judiciously controlling the morphology of nanomaterials or by utilizing the collective properties of nano-assembly systems. Finally, this review highlights the importance of matchup between catalysts and the redox couples, and points to crucial issues that should be addressed in the pursuit of developing low-cost and high-catalytic cathodes for DSCs.
