While many
attempts have been made in the recent past to improve the power conversion efficiencies of dye-sensitized solar cells (DSSCs), only a few reports can be found on the study of these cells using binary iodides in the gel polymer electrolyte. This paper reports the effect of using a binary mixture of (large and small cation) alkaline salts, in particular CsI and LiI, on the efficiency enhancement in DSSCs with gel polymer electrolytes. The electrolyte with the binary mixture of CsI:LiI = 1:1 (by weight) shows the highest ionic conductivity 2.9 × 10−3 S cm−1 at 25 °C. DC polarization measurements showed predominantly ionic behavior of the electrolyte. The density of charge carriers and mobility of mobile ions were calculated using a newly developed method. The temperature dependent behavior of the conductivity can be understood as due to an increase of both the density and mobility of charge carriers. The solar cell with only CsI as the iodide salt gave an energy conversion efficiency of ~3.9 % while it was ~3.6 % for the cell with only LiI. However, the electrolyte containing LiI:CsI with mass ratio 1:1 showed the highest solar cell performance with an energy conversion efficiency of ~4.8 % under the irradiation of one Sun highlighting the influence of the mixed cation on the performance of the cell. This is an efficiency enhancement of 23 %.