Effects of Driving Forces for Recombination and Regeneration on the Photovoltaic Performance of Dye-Sensitized Solar Cells using Cobalt Polypyridine Redox Couples

Dye-sensitized solar cells with open-circuit potentials above 1 V were obtained by employing the triphenylamine-based org. dye D35 in combination with cobalt phenanthroline redox couples. A series of cobalt bipyridine and cobalt phenanthroline complexes with different redox potentials were investigated to examine the dependence of the driving force for recombination and dye regeneration on the photovoltaic performance. The photovoltage of the devices was found to increase and the photocurrent to decrease with increasing redox potential of the complexes. The halftime for regeneration of the oxidized dye by cobalt tris(bipyridine) was about 20 μs, similar to that found for the iodide/triiodide redox couple, whereas regeneration kinetics became slower for cobalt complexes with less driving force for regeneration. A driving force for dye regeneration of 390 mV for cobalt(II/III) tris(5-chloro-1,10-phenanthroline) was found sufficient to regenerate more than 80% of the D35 dye mols., resulting in a conversion of incident photons-to-elec. current of above 80%. The photocurrent of the D35-sensitized solar cells using cobalt phenanthroline complexes decreased, however, with increasing Nernst potential of the redox couples, due to the increased recombination and the decreased regeneration rate consts.

Interfacial engineering for competitive Dye-Sensitized Solar Cells production

Natalie Flores Diaz

Renewable energy deployment and implementation of a circular economy will play a crucial role in decreasing CO2 emissions to meet the target from the Paris agreement. Dye-sensitized solar cells (DSSCs) can be designed in various colors and transparency for building-integrated photovoltaics (BIPV). This emerging technology has gained significant attention for its remarkably high power conversion efficiency (PCE) under indoor lighting up to 34%. To improve the performance of DSSCs, various approaches to study and reduce the interfacial electron recombination from the conduction band of the semiconductor to the electrolyte were implemented in this thesis. One of the approaches was the design of a tandem electrolyte containing two redox species, the radical AZADO (AZ+/0) and the [Co(bpy)3]2+/3+ complex. DSSCs with tandem electrolytes showed increased open-circuit voltage (VOC) up to 1009 mV and enhanced PCE of 9.15%. The VOC enhancement was determined to result from the higher redox potential of (AZ+/0) and the slower electron recombination rate. These findings demonstrate the advantages of employing tandem electrolytes to improve the VOC and overall performance of DSSCs. To decrease the solvent's volatility and the interfacial electron recombination in cobalt-based electrolytes, hyperbranched networks (HB) were designed through a click thiol-ene reaction between a thiol-siloxane and an acrylate monomer. The formed polymers were denoted HB1 (thiol-siloxane and PEGMA) and HB2 (thiol-siloxane and PEGMA). The addition of 20% of HB polymers to a cobalt-based electrolyte retained up to 98% of their initial weight until 150°C. The devices employing 10%(v/v) of HB1 attained the highest PCE under AM1.5 of 8.52%, comparable to 9.36% for the cobalt reference electrolyte. All the HB-electrolytes presented higher VOC values than the cobalt reference due to an upward shift in the CB of TiO2 and longer electron lifetimes. It was determined that the HB-polymers reduce the electron recombination and enhance the photovoltaic performance under low light intensity leading to a PCE of 23.19% under 1000 lux compared to 20.37% for the Co-reference. We then developed a new dye, R7, with a strong electron-donating PAH core and BPT2 as the central building block and a bulkier HF donor to decrease electron recombination at the interface TiO2/electrolyte. We found that in the presence of a copper electrolyte, the dye R7 outperformed devices with R6. EIS revealed that the bulky HF-donor introduction effectively suppressed the electron recombination between the TiO2 surface and the redox shuttle. Additionally, we employed a co-sensitized system of R7+Y123 to reach the outstanding parameters of JSC of 16.15 mAcm-2, VOC of 1035 mV, FF of 0.76 to achieve a top PCE of 12.7%. To the best of our knowledge, this is the highest for copper-based DSSCs using a blue photosensitizer. Lastly, the interfacial phenomena in DSSCs with carbon counter electrodes (CCEs) and copper-based electrolytes were studied to determine the feasibility of the production of monolithic DSSCs with copper-based hole-transporting materials. It was found that the electron transport in devices with CCEs is in the same order of magnitude as those with PEDOT. However, the devices with CCEs presented a decrease of 2 orders of magnitude in the recombination resistance, resulting in decreased VOC and JSC, leading to a PCE of 17% compared to 24.5% for PEDOT devices under 1000 lux illumination.

EPFL2021

Alternative redox systems for the dye-sensitized solar cell

Hervé Nusbaumer

Due to their high efficiencies and their potentially low production costs, dye-sensitized solar cells (DSSC) have attracted much attention during the last few years. The technology is based on a layer made of mesoscopic TiO2 film which significantly increases the optical path for light harvesting by the surface-anchored sensitizer molecules, whilst keeping an efficient contact with the electrolytic solution. These sensitizer molecules are often based on ruthenium polypyridyl complexes because of their high absorption coefficients in the visible, but any dye could be used to sensitize the semiconducting TiO2. The standard DSSC usually contain organic electrolytes with dissolved triiodide/iodide as the redox couple. Cells based on alternative electrolytes have been developed and were used in early DSSC designs, but showed somehow deceiving photovoltaic performances. Until now, endeavors to increase the photovoltage of dye-sensitized nanocrystalline cells by replacing iodide by a one-electron, outer-sphere redox couple with a more positive oxidation potential have not succeeded. This has been largely due to limitations imposed by the dark current and the slow diffusion of the alternate mediator. The work presented here focused on finding efficient alternative redox couples for the DSSC, able to rival the classical triiodide/iodide couple. The tested compounds were triarylamines, platinum complexes and cobalt complexes. Triarylamines and platinum complexes proved considerably less effective than the classical couple in term of photoelectrochemical efficiencies. Cobalt complexes however displayed far more interesting behavior. The experiments carried out demonstrated that the [Co(bip)2]3+/2+ complexes were the most suitable candidates to be used as redox mediators as their photoelectrochemical and kinetic behavior rivaled those of the triiodide/iodide redox couple. The system however had to be optimized to reach high efficiencies. Heteroleptic dyes incorporating long alkyl chains were found to be the most appropriate category of dye, boosting further the DSSC efficiency by reducing the dark current within the cells. Co-grafting the sensitizer and co-adsorbent led to an improved photovoltaic efficiency through the increased photocurrent. Silver addition in the dye solution also leads to a global improvement of the photovoltaic parameters. To avoid diffusion problems with the large molecules in the electrolyte, very thin nanocrystalline TiO2 layers had to be employed. A 3 μm thick nanoporous layer with a 3 μm scattering layer was found to be optimal. As cobalt complexes may undergo electrochemical processes on the SnO2 layer of the photoelectrode, a blocking layer of compact TiO2 was used to reduce the dark current. The electrochemical regeneration of the cobalt complexes with the SnO2 is not fast enough to support cell function and the counter electrode must be covered either with platinum or gold layer to ensure a good fill factor. The optimization of the electrolyte itself mainly concerned the choice of the solvent, the redox mediator concentration, the best degree of oxidation, the additives that can be used to improve the photovoltaic parameters and finally how to increase the redox couple solubility. The best efficiencies were achieved with an acetonitrile/ethylene carbonate (2:3) solvent mixture, with a total redox mediator concentration between 0.10 to 0.15 M. If 10% of this total concentration is oxidized, the current density reaches its maximum whilst having a negligible effect on the photovoltage. 4-tert-butylpyridine (TBP) and lithium perchlorate were tried as additives in the electrolyte, as TBP increases the photovoltage and Li+ the photocurrent. The optimal concentrations of these two additives was found to be around 0.05 M TBP and 0.1 M LiClO4 for an electrolyte having a total cobalt complex concentration of 0.1 M. Mass-transport within the cell is the limiting factor for high currents when using cobalt complexes as redox mediators. Attempts to reduce the solvent viscosity by using alternative solvents to the acetonitrile/ethylene carbonate mixture were not successful. One way to solve the diffusion problem was to irradiate the cell from the counter electrode side. This method works well at high irradiation intensities. Finally, reduction of the distance between the electrodes also enhances diffusion. The use of [Co(bip)2]3+/2+ complexes, with appropriate dyes and taking into account the optimizations already described above, allowed efficiencies of 8% under an irradiance of 95 W · m-2, as well as IPCEs over 80% at 540 nm to be obtained. At full sun, efficiencies of over 4% were reached, with short circuit current densities of 9.5 mA · cm-2 and open circuit voltages of the order of 860 mV.

EPFL2004

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

The aim of this work was to develop new, organic dyes, capable of harvesting photons in the red to near-IR region of the spectrum. A series of squaraine and tricarbocyanine dyes were produced and characterised and their optical and redox properties studied. The results of initial photovoltaic tests, followed by optimisations of cell performance, have also been presented. These clearly demonstrate the effectiveness of these dyes in solar cells. A total of 12 new squaraine dyes were successfully synthesised, seven of which were tested in "dye-sensitised" solar cells. The efficiencies ranged from 1.2%-3.7%, for the best dye [B1]. It was concluded that enhanced performance could be achieved in the presence of chenodeoxycholic acid (CDCA) and tetrabutylpyridine (TBP). These additives both help to prevent aggregation and increase the cell potential, limiting charge collection losses and enhancing performance. Three new tricarbocyanine dyes were also synthesised, two of which were used in solar cells. Unfortunately, due to the interaction of [B12] with the electrolyte, the dye proved to be unstable, as both the absorption maxima in UV-vis and fluorescence emission wavelengths were shifted to higher energies. Thus, the red response of the dye was significantly reduced and photovoltaic performance hindered. A limited photo-response of [B14] was also seen, although this dye appeared to be very stable in the presence of the electrolyte. To deduce the possible reasons for the poor performance of these dyes, their optical and electrochemical properties were investigated. Thus, cyclic voltametry was employed to identify the redox potentials of the dyes and their charge injection and recombination dynamics were studied through nanosecond time-resolved transient laser spectroscopy. It was concluded that the dyes theoretically possess the ideal characteristics for solar cell function and that the problem of [B14] lay in the purity of the dye. [B14] proved to be very difficult to purify as the dye was unstable in solution and decomposed on the columns employed in chromatography. Fortunately the dye appeared to be stable in the presence of an electrolyte when adsorbed on TiO2. The dye gave an IPCE of 12% between 800 – 900nm, which is particularly impressive, especially if the purity of the dye is considered. A new method of purification must be found however, if photovoltaic performance is to be enhanced. Finally, the effects of a compact blocking layer on device performance were studied. It was clearly demonstrated that a compact layer was essential. This was investigated and a relationship between the structure of the dye and the necessity of the blocking layer was established.

EPFL2006