Binary counter ion effects and dielectric behavior of iodide ion conducting gel-polymer electrolytes for high-efficiency quasi-solid-state solar cells.

A series of highly efficient quasi-solid-state dye-sensitized solar cells (DSCs) is prepared by harnessing the binary cation effect and positive effects of the selected performance enhancers of gel-polymer electrolytes. The new electrolyte is composed of polyacrylonitrile polymer, tetra-hexylammonium iodide (Hex4NI) and KI binary salts as well as 4-tertbutylpyridine and 1-butyl-3-methylimidazolium iodide performance enhancers. The charge transport in the series of electrolytes is thermally activated and, accordingly, the temperature dependence of conductivity follows the VTF behavior. The enhancement of conductivity is observed with an increasing mass fraction of KI and decreasing mass fraction of Hex4NI, while the total mass fraction of salts in the electrolyte is kept unchanged. The highest conductivity of 3.74 mS cm-1 at ambient temperature is shown by the sample containing KI only (without Hex4NI) at all the temperatures. The effects of dielectric polarization of the electrolytes are studied by analyzing the frequency dependence of the real and the imaginary parts of the AC conductivity in detail. Appropriate and reproducible cell construction are assured by efficiencies of above 5% exhibited by all the quasi-solid-state DSCs assembled using double-layered TiO2 photo-electrodes and the new electrolyte series. Besides, highlighting the mixed cation effect, the cells with mixed salts exhibited efficiencies greater than 6%. An impressively high efficiency of 7.36% was shown by the DSC prepared with electrolyte containing 75 wt% KI and 25 wt% Hex4NI. This study reveals that the salt combination of KI and Hex4NI, which has not been reported before, is a suitable binary iodide salt mixture to prepare highly efficient DSCs. The replacement of tetra-hexylammonium ions by K+ ions improves the charge transport in the electrolyte; however, the best solar cell performance is shown by the mixed salt system with 75 wt% KI and 25 wt% Hex4NI, which is not the highest conductivity composition. Therefore, the exhibited high efficiency of 7.36% is evidently due to the binary cation effect.

Effect of the alkaline cation size on the conductivity in gel polymer electrolytes and their influence on photo electrochemical solar cells.

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.

Efficiency enhancement in dye sensitized solar cells using gel polymer electrolytes based on a tetrahexylammonium iodide and MgI2 binary iodide system.

Quasi-solid-state dye-sensitized solar cells have drawn the attention of scientists and technologists as a potential candidate to supplement future energy needs. The conduction of iodide ions in quasi-solid-state polymer electrolytes and the performance of dye sensitized solar cells containing such electrolytes can be enhanced by incorporating iodides having appropriate cations. Gel-type electrolytes, based on PAN host polymers and mixture of salts tetrahexylammonium iodide (Hex4N(+)I(-)) and MgI2, were prepared by incorporating ethylene carbonate and propylene carbonate as plasticizers. The salt composition in the binary mixture was varied in order to optimize the performance of solar cells. The electrolyte containing 120% Hex4N(+)I(-) with respect to weight of PAN and without MgI2 showed the highest conductivity out of the compositions studied, 2.5 × 10(-3) S cm(-1) at 25 °C, and a glass transition at -102.4 °C. However, the electrolyte containing 100% Hex4N(+)I(-) and 20% MgI2 showed the best solar cell performance highlighting the influence of the cation on the performance of the cell. The predominantly ionic behaviour of the electrolytes was established from the dc polarization data and all the electrolytes exhibit iodide ion transport. Seven different solar cells were fabricated employing different electrolyte compositions. The best cell using the electrolyte with 100% Hex4N(+)I(-) and 20% MgI2 with respect to PAN weight showed 3.5% energy conversion efficiency and 8.6 mA cm(-2) short circuit current density.