Driven by the tremendous opportunities offered by dye solar cells technology in terms of building integration, a new generation of smart multifunctional photoelectrochemical cells has the potential to attract the interest of a rapidly growing number of research institutions and industrial companies. Photovoltachromic devices are capable to produce a smart modulation of the optical transmittance and, at the same time, to generate electrical power by means of solar energy conversion. In this work, a specifically designed bifunctional counterelectrode has been realized by depositing a C-shaped platinum frame which bounds a square region occupied by a tungsten oxide (WO3) film onto a transparent conductive substrate. These two regions have been electrically separated to make possible distinct operations on one or both of the available circuits. Such an unconventional counterelectrode makes it possible to achieve a twofold outcome: a smart and fast-responsive control of the optical transmittance and a relatively high photovoltaic conversion efficiency. In particular we investigated the effect of the electrolyte composition on both photoelectrochromic and photovoltaic performances of such devices by systematically tuning the iodide content in the electrolyte. The best result was obtained by filling the cell with an iodine concentration of 0.005 M: a coloration efficiency of 61.10 cm2C−1 at a wavelength of 780 nm and, at the same time, a photovoltaic conversion efficiency of 6.55% have been reported.
