Quasi-solid state polymer electrolytes for dye-sensitized solar cells: Effect of the electrolyte components variation on the triiodide ion diffusion properties and charge-transfer resistance at platinum electrode

Quasi-solid state polymer electrolytes have been prepared from poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as gelator for 1-ethyl-3-methylimidazolium based ionic liquids (with anions like trifluoromethanesulfonate [EMIM][TfO], bis(trifluoromethanesulfonyl)imide [EMIM][Tf2N]) and polyacrylonitrile (PAN) for gelation of 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] as well as I−/I3− as the redox couple. All electrolytes exhibit high ionic conductivity in the range of 10− 3 S/cm. The effect of gelation, redox couple concentration, I−/I3− ratio, choice of cations and additives on the triiodide diffusion and charge-transfer resistance of the platinum/electrolyte interface (Rct) were studied. The apparent diffusion coefficient of triiodide ion (D(I3−)) at various iodide/triiodide ratios in liquid and gelified electrolytes has been calculated from measurements of the diffusion limited current (Ilim) in electrochemical cell resembling the set-up of a dye-sensitized solar cell. The charge-transfer resistance of the platinum/electrolyte interface as well as the capacitance of the electrical double layer (Cdl) have been calculated from impedance measurements. Electrolytes with reduced content of polymer (2.5 wt.%) were doped with Al2O3 particles of different sizes (50 nm, 300 nm, 1 μm). The dispersion of the particles proceeds by speedy stirring of the hot electrolyte and the addition of PAN provides a homogeneous suspension. The addition of Al2O3 particles causes a slight increase of the triiodide diffusion constants. Furthermore the suggested enhancement of the charge transfer rate shows a dependence on the size of the particles.