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.

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In this study, the electrical, dielectric and morphological analysis of composite solid polymer electrolytes containing polyethylene oxide, alumina nano-fillers and tetrapropylammonium iodide are conducted. The temperature dependence of conductivity shows activation energy of 0.23, 0.20 and 0.29 eV for electrolytes containing 0, 5 and 15 wt.% alumina, respectively, when data fitted to the Arrhenius equation. These activation energy values are in good agreement with those determined from dielectric measurements. The result confirms the fact that conductivity is activated by both the mobility and the charge carrier density. The conductivity isotherms demonstrated the existence of two peaks, at 5 and 15 wt.% Al 2 O 3 composition. The highest conductivity values of 2.4 × 10 −4 , 3.3 × 10 −4 and 4.2 × 10 −4 S cm −1 are obtained for the sample with 5 wt.% Al 2 O 3 at 0, 12 and 24°C, respectively, suggesting an enhancement of conductivity compared with that of alumina free samples.

Performance of dye-sensitized nano-crystalline TiO 2 thin film-based photo-electrochemical solar cells (PECSCs) containing gel polymer electrolytes is largely governed by the nature of the cation in the electrolyte. Dependence of the photovoltaic performance in these quasi-solid state PECSCs on the alkaline cation size has already been investigated for single cation iodide salt-based electrolytes. The present study reports the ionic conductivity dependence on the nature of alkaline cations (counterion) in a gel polymer electrolyte based on binary iodides. Polyacrylonitrile-based gel polymer electrolyte series containing binary iodide salts is prepared using one of the alkaline iodides (LiI, NaI, KI, RbI, and CsI) and tetrapropylammonium iodide (Pr 4 NI

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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 TiO 2 film sensitized with two types of dye sensitizers, namely N719 (Ruthenizer 535-bisTBA) and N3 (Ruthenizer 535) in order to compare their performance. Quasisolid-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 (Pr 4 NI), 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.