The effect of electrolyte filling method on the performance of dye-sensitized solar cells

The effect of electrolyte filling method on the performance of the dye-sensitized solar cells is investigated with the segmented cell method, a recent technique which is very simple but effective as it can be used to examine all the photovoltaic characteristics. The electrolyte filling techniques compared were single injection, which is typically used in small laboratory cells, and pumping the electrolyte through the cell several times, which is often used for larger cells and modules. Significant photovoltage and photocurrent variations occur with the repeated pumping of the electrolyte in the cell preparation. Transient and charge extraction measurements confirmed that the differences in open circuit voltage were due to the shifts of the TiO2 conduction band and time correlated single photon counting confirmed that the reduction of short circuit current was largely due to reduced electron injection correlated with the increasing conduction band edge in the studied cases. This was interpreted as an effect of molecular filtering by the TiO2 causing an accumulation of electrolyte additives (4-tert-butylpyridine and benzimidazole) near the electrolyte filling hole, the concentration of which increased with repeated pumping of the electrolyte. Interestingly, spatial variations were seen not only in the relative TiO2 conduction band energy but also in the density of trap states. In this contribution it is demonstrated how the changes in the conduction band can be separated from the changes in the density of trap states which is an essential for the correct interpretation of the data.Peer reviewe

Do Counter Electrodes on Metal Substrates Work with Cobalt Complex Based Electrolyte in Dye Sensitized Solar Cells?

Yes. Testing 7 different metals as a substrate for a counter electrode in dye sensitized solar cells (DSSC) showed that some metals can be a good option for use with cobalt electrolyte. It was found that Stainless steels 304 and 321 as well as Ni and Ti suit well to the counter electrodes in DSSCs with cobalt electrolyte. In these 4 cases both the efficiency and the lifetime were similar to the reference cells on conducting glass substrates. In contrast, the cells with Al, Cu and Zn substrates suffered from both a low efficiency and a poor stability. These three metals had clear marks of corrosion such as apparent corrosion products in the aged cells. Additionally, we also investigated how the different types of catalyst materials perform in the case of a metal counter electrode (stainless steel 304) with cobalt electrolyte in comparison to reference glass cells. Among the 5 different catalyst layers the best results for stainless steel electrode were achieved with low temperature platinization whereas polymer catalysts poly(3,4-ethylenedioxythiophene)-p-toluenesulfone and poly(3,4-ethylenedioxythiophene)-polystyrenesulfone that worked well on the glass worked very poorly on the metal.Peer reviewe

Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO2: Separation of Electronic and Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets during J-V Hysteresis

Methylammonium lead iodide (MAPI) cells of the design FTO/sTiO2/ mpTiO2/MAPI/Spiro-OMeTAD/Au, where FTO is fluorine-doped tin oxide, sTiO2 indicates solid-TiO2, and mpTiO2 is mesoporous TiO2, are studied using transient photovoltage (TPV), differential capacitance, charge extraction, current interrupt, and chronophotoamperometry. We show that in mpTiO2/MAPI cells there are two kinds of extractable charge stored under operation: a capacitive electronic charge (&sim;0.2 &mu;C/ cm2) and another, larger charge (40 &mu;C/cm2), possibly related to mobile ions. Transient photovoltage decays are strongly double exponential with two time constants that differ by a factor of &sim;5, independent of bias light intensity. The fast decay (&sim;1 &mu;s at 1 sun) is assigned to the predominant charge recombination pathway in the cell. We examine and reject the possibility that the fast decay is due to ferroelectric relaxation or to the bulk photovoltaic effect. Like many MAPI solar cells, the studied cells show significant J&minus;V hysteresis. Capacitance vs open circuit voltage (Voc) data indicate that the hysteresis involves a change in internal potential gradients, likely a shift in band offset at the TiO2/MAPI interface. The TPV results show that the Voc hysteresis is not due to a change in recombination rate constant. Calculation of recombination flux at Voc suggests that the hysteresis is also not due to an increase in charge separation efficiency and that charge generation is not a function of applied bias. We also show that the J&minus;V hysteresis is not a light driven effect but is caused by exposure to electrical bias, light or dark.</div

Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO2: Separation of Electronic and Chemical Charge Storage

Methylammonium lead iodide (MAPI) cells of the design FTO/sTiO2/ mpTiO2/MAPI/Spiro-OMeTAD/Au, where FTO is fluorine-doped tin oxide, sTiO2 indicates solid-TiO2, and mpTiO2 is mesoporous TiO2, are studied using transient photovoltage (TPV), differential capacitance, charge extraction, current interrupt, and chronophotoamperometry. We show that in mpTiO2/MAPI cells there are two kinds of extractable charge stored under operation: a capacitive electronic charge (&sim;0.2 &mu;C/ cm2) and another, larger charge (40 &mu;C/cm2), possibly related to mobile ions. Transient photovoltage decays are strongly double exponential with two time constants that differ by a factor of &sim;5, independent of bias light intensity. The fast decay (&sim;1 &mu;s at 1 sun) is assigned to the predominant charge recombination pathway in the cell. We examine and reject the possibility that the fast decay is due to ferroelectric relaxation or to the bulk photovoltaic effect. Like many MAPI solar cells, the studied cells show significant J&minus;V hysteresis. Capacitance vs open circuit voltage (Voc) data indicate that the hysteresis involves a change in internal potential gradients, likely a shift in band offset at the TiO2/MAPI interface. The TPV results show that the Voc hysteresis is not due to a change in recombination rate constant. Calculation of recombination flux at Voc suggests that the hysteresis is also not due to an increase in charge separation efficiency and that charge generation is not a function of applied bias. We also show that the J&minus;V hysteresis is not a light driven effect but is caused by exposure to electrical bias, light or dark.</div

The Mechanism of Iodine Reduction by TiO₂ Electrons and the Kinetics of Recombination in Dye-Sensitized Solar Cells

Electron transfer from TiO₂ to iodine/iodide electrolytes proceeds via reduction of either I₃^– or uncomplexed I₂ (free iodine), but which route predominates has not previously been determined. By measurement of the electron lifetime while independently varying free iodine or I₃^– concentrations, we find the lifetime is correlated with free-iodine concentration and independent of I₃^– concentration. This trend supports the hypothesis that electron recombination to the electrolyte occurs predominantly by iodine reduction rather than reduction of triiodide

Rediscovering a Key Interface in Dye-Sensitized Solar Cells: Guanidinium and Iodine Competition for Binding Sites at the Dye/Electrolyte Surface

We propose a new mechanism by which the common electrolyte additive guanidinium thiocyanate (GdmSCN) improves efficiency in dye-sensitized solar cells (DSSCs). We demonstrate that binding of Gdm(+) to TiO2 is weak and does not passivate recombination sites on the TiO2 surface as has been previously claimed. Instead, we show that Gdm(+) binds strongly to the N719 and D131 dyes and probably to many similar compounds. The binding of Gdm(+) competes with iodine binding to the same molecule, reducing the surface concentration of dye-I-2 complexes. This in turn reduces the electron/iodine recombination rate constant, which increases the collection efficiency and thus the photocurrent. We further observe that GdmNO(3) can increase efficiency more than the current Gdm(+) source, GdmSCN, at least in some DSSCs. Overall, the results point to an improved paradigm for DSSC operation and development. The TiO2/electrolyte surface has long been held to be the key interface in DSSCs. We now assert that the dye layer/electrolyte interaction is at least, and probably more, important

What makes dye cells tick, or kick the bucket? Injection, regeneration, and collection efficiencies in new, old, dry, and wet dye sensitized solar cells

DSC electrolytes tolerant of water are demonstrate (figure 1). Some with surprising stability (figure 2). TAS data of complete cells allows determination of the rate constants for regeneration of S+ and electron recombination with S+ (figure 3). Luminescence lifetime (figure 4) of a large variety of cells, light soaked or thermally treated, indicate that the photocurrent can be explained by slow injection. We address diffusion length, its definition, determination, and relation to the empirical optimum thickness for DSCs

Water-Based Electrolytes for Dye-Sensitized Solar Cells

Stable and efficient dye-sensitized solar cells based on water-containing electrolytes are shown. For water contents up to 40%, no decrease in efficiency is seen. The cells are demonstrated to be stable for long periods of continuous illumination.This work lays a foundation for the further development of water-based cells for commercial production

The mechanism behind the beneficial effect of light soaking on injection efficiency and photocurrent in dye sensitized solar cells

Electrical and luminescence characterization was performed on 16 dye sensitized solar cells with different formulations, from different industrial and academic sources. Most of the cells were fabricated in pre-industrial pilot lines. The cells were put through a light soaking period up to 150 hours and then re-characterized. The results show the commonly observed increase in J sc with light soaking is due to a decrease in the conduction band energy (with respect to the electrolyte) and an increase in the injection rate and efficiency. The strong correlation between the luminescence decay lifetime (&lt;200 ps to 5 ns) and the photocurrent (7 to 13 mA cm -2) shows that the luminescence decay is a useful monitor of injection rates in these cells. The very slow injection shown by some cells implies substantial losses at the injection step. The data point to a need to understand and improve the TiO 2 processing and dyeing conditions in the industrial setting as well as the need to focus injection studies on the full range of dynamics present in the cell