Photopolymerisation of acrylic monomers for quasi-solid dye-sensitized solar cells

As a feasible option for photovoltaic technology to meet the growing energy demand, dye-sensitized solar cells (DSSCs) have attracted much attention due to their low cost, ease of fabrication and good performance. Standard DSSCs use a liquid electrolyte, usually based on the I-/I3- redox couple in an organic solvent. This setting leads to high efficiencies, but it can result in relevant technological drawbacks associated with poor long-term stability, difficulty in robust and hermetic sealing, electrolyte evaporation/leakage, permeability to H2O/O2. A very promising and common skill used to solve these problems is the attempt to replace the liquid electrolyte with a quasi-solid or solid electrolyte. Indeed, several efforts have been made to replace the liquid redox mediator by polymer electrolytes, including liquid solidified with physically cross-linked gelators and gel-polymer electrolytes [1]. In particular, to overcome the drawbacks of conventional polymerization techniques (long reaction times, use of solvents, solubilization/separation steps), a great possibility is provided by the free-radical photo-polymerization process. In fact, this technology is rapid, inexpensive, consistent with the main canons of green-chemistry and could be easily transferred to industrial scale [2]. In this study, we fabricated cross-linked thin films starting from bisphenol A ethoxylate dimethacrylate (BEMA) and polyethylene glycol methyl ether methacrylate (PEGMA). Self standing membranes (100 µm thick) were obtained by UV irradiating the mixtures for 4 min and, then, activated by soaking into a liquid electrolyte solution (NaI/I2/acetonitrile). The procedure is depicted in Figure 1. In order to optimize the experimental conditions, a chemometric approach (at the best of our knowledge for the first time in the DSSC area) was selected. Two designs of experiments (DoE) were planned. At first, two-level fractional factorial design (resolution V) with five factors was used to eliminate unimportant factors. From the data analysis, BEMA:PEGMA ratio and NaI/I2 concentration were proved to be significant factors on DSSC performance; conversely, swelling time, propylene carbonate (as plasticizer) and LiClO4 salt (as additive) were found to be not relevant. Afterwards, central composite face centered design (CCF) was employed to investigate the simultaneous effect of the two relevant factors (Figure 2). The set of experiments we carried out allowed us to produce a quasi-solid DSSC with durable excellent efficiency as high as 5.41 %. In addition, an accurate characterization of the photo-cured membranes and the photo-electrochemical device was performed and will be here thoroughly discussed.