Improving performance of copper(I)-based dye sensitized solar cells through I3−/I− electrolyte manipulation

• Effects of changing I−/I3− electrolyte composition on performance of Cu-based DSSCs.
• Low concentrations of I2 and omission of LiI are optimal.
• 1-Butyl-3-methylimidazolium acts as the source of I−.
• Addition of GNCS and/or TBP reduces recombination rates in DSSCs with a copper dye.

The performances of dye-sensitized solar cells (DSSCs) containing a heteroleptic bis(diimine)copper(I) dye and an I3−/I− liquid electrolyte have been investigated as a function of the electrolyte composition. Starting from a standard electrolyte with LiI (0.1 M), I2 (0.05 M), 1-butyl-3-methylimidazolium (BMII) ionic liquid (0.6 M), 1-methylimidazole additive (0.5 M) in 3-methoxypropionitrile (MPN), a series of ten electrolytes was initially screened; the solvent, additives, concentration of I2, and sources (LiI and/or BMII) and concentrations of I− were varied. The highest short-circuit current densities (JSC = 7.85 and 7.60 mA cm−2) and photoconversion efficiencies (η = 2.64 and 2.70% relative to 6.56 and 6.11% for two N719 references) were observed for DSSCs with an electrolyte comprising I2 (0.03 M), BMII (0.6 M), 4-tert-butylpyridine (TBP, 0.4 M) and guanidinium thiocyanate (GNCS, 0.1 M) in MPN solvent; no LiI was added. This composition was further optimized by varying the amounts of TBP and GNCS. A low concentration of I2 (0.015 M) is optimal. The presence or absence of GNCS has little effect on overall DSSC performance, but increasing the concentration of TBP is detrimental to DSSC performance, and an absence of TBP is beneficial. Open-circuit voltage decay (OCVD) measurements confirm that the addition of GNCS and/or TBP reduces recombination rates at the TiO2-dye interface. The best DSC parameters obtained for the copper(I)-based dye were JSC = 7.80 mA cm−2, open-circuit voltage (VOC) = 501 mV and η = 2.76% (relative to 6.72% for N719).

The photoconversion efficiency, η of a phosphonic acid-anchored copper(I) dye in a DSC is greatly affected by the I3−/I− electrolyte composition; optimal η is achieved with [I2] = 0.015 M and the only I− source being BMII in 3-methoxypropionitrile.Figure optionsDownload as PowerPoint slide