Iodide ion conducting electrolytes are intensively studied as effectual electrolytes for dye-sensitized solar cells (DSSCs). However, the nature and concentration of the counter-ion (cation) in the electrolyte exert a profound influence on the performance of the thin film meso-porous TiO2 based DSSCs. A series of gel electrolytes containing the alkaline iodides LiI, NaI, KI, RbI and CsI and polyacrylonitrile (PAN) were fabricated together with the non-volatile plasticizers ethylene carbonate (EC) and propylene carbonate (PC). A similar series was fabricated with the inclusions of performance enhancers (additives) tetrapropylammonium iodide (Pr4NI), the ionic liquid 1-methyl-3-propyl imidazolium iodide (MPII) and 4-tert-butylpyridine (4TBP). The ionic conductivity of the electrolytes was studied in order to investigate its dependence on the nature of the alkaline cation in presence or absence of additives. The conductivities were higher for the electrolytes with the larger cations, namely K+, Rb+ and Cs+. A significant conductivity enhancement was observed in presence of the additives, and this effect was especially noticeable for samples with the smaller cations. The highest conductivity for electrolytes with additives, 3.96mScm−1 at 25°C, is exhibited by KI containing samples.

Dye sensitized solar cells offer a low cost alternative technology for solar energy harvesting. However, there are long term stability issues connected with these cells due to the liquid electrolytes normally used. Gel or solid polymer electrolytes which do not contain volatile solvents have been used in this investigation in order to alleviate these problems. Two types of solar cells were assembled using a double layered TiO2 film sensitized with two types of dye sensitizers, namely N719 (Ruthenizer 535-bisTBA) and N3 (Ruthenizer 535) in order to compare their performance. Quasi-solid-state electrolytes based on PAN (polyacrylonitrile) as the host polymer and CsI as the iodide salt were prepared by incorporating ethylene carbonate (EC) and propylene carbonate (PC) as plasticizers. The conductivity of the electrolyte was further improved by adding tetrapropylammonium iodide (Pr4NI), 1-methyl 3-propyl imidazolium iodide (MPII) and 4-tert-butylpyridine (4TBP). The incorporation of these additives resulted in 17% enhancement in ionic conductivity. This improved electrolyte was used to fabricate the solar cells with N3 and N719 dyes. The efficiency of the N3 dye based solar cell was 3.85% whereas the efficiency of the N719 dye based solar cell was 4.14% representing a significant efficiency enhancement by 7.53% by the N719 dye. In addition, due to additives the solar cell efficiency has enhanced by 19% compared to the solar cell without any additive.

Performance enhancers improved the efficiency in LiI based and RbI based solar cells by 449 and 35.7% respectively.

The nature and concentration of cationic species in the electrolyte exert a profound influence on the efficiency of nanocrystalline dye-sensitized solar cells (DSSCs). A series of DSSCs based on gel electrolytes containing five alkali iodide salts (LiI, NaI, KI, RbI and CsI) and polyacrylonitrile with plasticizers were fabricated and studied, in order to investigate the dependence of solar cell performance on the cation size. The ionic conductivity of electrolytes with relatively large cations, K(+), Rb(+) and Cs(+), was higher and essentially constant, while for the electrolytes containing the two smaller cations, Na(+) and Li(+), the conductivity values were lower. The temperature dependence of conductivity in this series appears to follow the Vogel-Tamman-Fulcher equation. The sample containing the smallest cation shows the lowest conductivity and the highest activation energy of ∼36.5 meV, while K(+), Rb(+) and Cs(+) containing samples show an activation energy of ∼30.5 meV. DSSCs based on the gel electrolyte and a TiO2 double layer with the N719 dye exhibited an enhancement in the open circuit voltage with increasing cation size. This can be attributed to the decrease in the recombination rate of electrons and to the conduction band shift resulting from cation adsorption by TiO2. The maximum efficiency value, 3.48%, was obtained for the CsI containing cell. The efficiencies shown in this study are lower compared to values reported in the literature, and this can be attributed to the use of a single salt and the absence of other additives, since the focus of the present study was to analyze the cation effect. The highest short circuit current density of 9.43 mA cm(-2) was shown by the RbI containing cell. The enhancement of the solar cell performance with increasing size of the cation is discussed in terms of the effect of the cations on the TiO2 anode and ion transport in the electrolyte. In liquid electrolyte based DSSCs, the short circuit current density has been reported to decrease with the increasing size of the cation. However, in this work, it follows an opposite trend highlighting a major difference between liquid and quasi-solid electrolytes on the solar cell performance.