A conceptually new polymer electrolyte for dye-sensitized solar cells is reported and investigated. The benefits of using this type of electrolyte based on ionic liquid mixtures (ILMs) and room temperature ionic liquids are highlighted. Impedance spectroscopy and transient electron measurements have been used to elucidate the background of the photovoltaic performance. Even though larger recombination losses were noted, the high ion mobility and conductivity induced in the ILMs by the added polymer result in enhanced overall conversion efficiencies.
Recently, cobalt redox electrolyte mediators have emerged as a promising alternative to the commonly used iodide/triiodide redox shuttle in dye-sensitized solar cells (DSCs). Here, we report the successful use of a new quasi-liquid, polymer-based electrolyte containing the Co3+/Co2+ redox mediator in 3-methoxy propionitrile solvent in order to overcome the limitations of high cell resistance, low diffusion coefficient and rapid recombination losses. The performance of the solar cells containing the polymer based electrolytes increased by a factor of 1.2 with respect to an analogous electrolyte without the polymer. The performances of the fabricated DSCs have been investigated in detail by photovoltaic, transient electron measurements, EIS, Raman and UV-vis spectroscopy. This approach offers an effective way to make high-performance and long-lasting DSCs.
In this work, we have designed and synthesized a novel molecular material, BDT-C1, in which the core unit, benzodithiophene (BDT), was functionalized by thiophene (TP) and benzo-[c][1,2,5]-thiadiazole (BTZ) derivatives to generate extended pi-conjugation. BDT-C1 shows high hole mobility and high conductivity in its pristine form, in combination with appropriate energy level alignment with respect to [CH3NH3]PbI3 and PC70BM, qualifying the material as a good candidate for application both in perovskite solar cells (PSCs) as dopant-free hole transport material (HTM) and in OSCs as donor material. The champion PSCs based on BDT-C1 show an average conversion efficiency (PCE) of 13.4% (scan forward: 13.9%; scan backward: PCE=12.9%, scan rate: 10 mV/s). Although the average efficiency obtained is slightly lower than that of reference devices based on the well-known doped HTM Spiro-OMeTAD (13.7%), the BDT-C1 based devices exhibit better stability. Moreover, BDT-C1 as a donor material in OSCs also shows good performance in combination with PC70BM as acceptor material, and an efficiency of 6.1% was obtained. The present results demonstrate that BDT-C1 works well as both donor material in OSCs as well as dopant-free HTMs for efficient PSCs.
Dipicolinic acidwas investigated as a new anchoring group for DSSCs. A pilot dye (PD2) bearing this new anchoring group was found to adsorb significantly stronger to TiO2 than its cyanoacrylic acid analogue. The electrolyte composition was found to have a strong effect on the photoelectrochemical properties of the adsorbed dye in the device, allowing the dye LUMO energy to be tuned by 0.5 eV. Using a pyridine-free electrolyte, panchromatic absorption of the dye on TiO2 extending to 900 nm has been achieved. Solar cells using PD2 and a Co(bpy)(3) based electrolyte showed unique stability under simulated sunlight and elevated temperatures.
The long-term outdoor durability of dye-sensitized solar cells (DSSCs) is still a challenging issue for the large-scale commercial application of this promising photovoltaic technique. In order to study the degradation mechanism of DSSCs, ageing tests under selected accelerating conditions were carried out. The electrolyte is a crucial component of the device. The interactions between the electrolyte and other device components were unraveled during the ageing test, and this is the focus of this thesis. The dynamics and the underlying effects of these interactions on the DSSC performance were studied.
Co(bpy)32+/3+-mediated solar cells sensitized by triphenylamine-based organic dyes are systems of main interest. The changes with respect to the configuration of both labile Co(bpy)32+ and apparently inert Co(bpy)33+ redox complexes under different ageing conditions have been characterized, emphasizing the ligand exchange problem due to the addition of Lewis-base-type electrolyte additives and the unavoidable presence of oxygen. Both beneficial and adverse effects on the DSSC performance have been separately discussed in the short-term and long-term ageing tests. The stability of dye molecules adsorbed on the TiO2 surface and dissolved in the electrolyte has been studied by monitoring the spectral change of the dye, revealing the crucial effect of cation-based additives and the cation-dependent stability of the device photovoltage. The dye/TiO2 interfacial electron transfer kinetics were compared for the bithiophene-linked dyes before and after ageing in the presence of Lewis base additives; the observed change being related to the light-promoted and Lewis-base-assisted performance enhancement. The effect of electrolyte co-additives on passivating the counter electrode was also observed. The final chapter shows the effect of electrolyte composition on the electrolyte diffusion limitation from the perspectives of cation additive options, cation concentration and solvent additives respectively. Based on a comprehensive analysis, suggestions have been made regarding lithium-ion-free and polymer-in-salt strategies, and also regarding cobalt complex degradation and the crucial role of Lewis base additives. The fundamental studies contribute to the understanding of DSSC chemistry and provide a guideline towards achieving efficient and stable DSSCs.
A significant improvement in the long-term stability for cobalt-based dye-sensitized solar cells (DSCs) under light-soaking conditions has been achieved by optimization of the composition of tris(2,2'-bipyridine) Co(II)/Co(III) electrolytes. The effects of component exchanges and changes were also studied during the optimization process.
A significant increase in the photocurrent generation during light soaking for solar cells sensitized by the triphenylamine-based D-pi-A organic dyes (PD2 and LEG1) and mediated by cobalt bipyridine redox complexes has been observed and investigated. The crucial role of the electrolyte has been identified in the performance improvement. Control experiments based on a pretreatment strategy reveals TBP as the origin. The increase in the current and IPCE has been interpreted by the interfacial charge-transfer kinetics studies. A slow component in the injection kinetics was exposed for this system. This change explains the increase in the electron lifetime and collection efficiency. Photoelectron spectroscopic measurements show energy shifts at the dye/TiO2 interface, leading us to formulate a hypothesis with respect to an electrolyte induced dye reorganization at the surface.
The precipitation of solid compounds from model electrolytes for liquid dye-sensitized solar cells has a story to tell regarding decomposition processes to be expected in such systems. Of course, the crystal lattice energy for a specific crystalline compounds plays a role in what compound that will eventually precipitate, but the compounds nevertheless serve as indicators for what type of processes that take place in the solar cell electrolytes upon ageing. From the compounds isolated in this study we learn that both ligand exchange processes, double-salt precipitation and oxidation are degradation processes that should not be overlooked when formulating efficient and stable electrolytes for this type of electrochemical system.
The electrolyte composition has a significant effect on the performance and stability of cobalt-based, dye-sensitized solar cells (DSSCs). The stability of DSSCs incorporating Co(II/III) tris(bipyridine) redox mediator has been investigated over 1000 h under full solar irradiation (with UV cutoff) at a temperature of 60 °C, the main focus being on monitoring the photovoltaic performance of the device and analyzing the internal charge-transfer dynamics in the presence of different cation coadditives (preferably added as tetracyanoborate salts). A clear cation-dependence is shown, not only of the early light-induced performance but also of the long-term photostability of the photovoltage of the device. These light-induced changes, which are attributed to the promotion of electron injection and less electron recombination loss, by transient spectral and electrochemical studies at the TiO2/dye/electrolyte interface, indicate that the main cation effects involve the TiO2 surface electric field and energy-state distribution. By examining the stability of adsorbed and solvated dye during aging, it has been found that the dye photodegradation is probably responsible for the decline in the photovoltage and that this is extremely dependent on the nature of the cation coadditives in the electrolyte. It is therefore suggested that optimization of the electrolyte cation composition is essential for improving the stability of cobalt-based DSSCs.
Lithium-ion-free tris(2,2 '-bipyridine) Co(ii/iii)-mediated electrolytes have previously been proposed for long-term stable dye-sensitized solar cells (DSSCs). Such redox systems also offer an impressive DSSC performance improvement under light soaking exposure, manifested by an increase in photocurrent and fill factor without the expense of decreasing photovoltage. Kinetic studies show that charge transfer and ion diffusion at the electrode/electrolyte interface are improved due to the light exposure. Control experiments reveal that the light effect is unambiguously associated with electrolyte components, [Co(bpy)(3)](3+) and the Lewis-base additive tert-butylpyridine (TBP). Electrochemical and spectroscopic investigation of the [Co(bpy)(3)](3+)/TBP mixtures points out that the presence of TBP, which retards the electrolyte diffusion, however causes an irreversible redox reaction of [Co(bpy)(3)](3+) upon light exposure that improves the overall conductivity. This discovery not only provides a new strategy to mitigate the typical J(sc)-V-oc trade-off in Co(ii/iii)-mediated DSSCs but also highlights the importance of investigating the photochemistry of a photoelectrochemical system.
A novel blue-colored organic donor-pi-acceptor sensitizer, the so-called MKA16 dye, has been employed to construct solid-state dye-sensitized solar cells (ssDSSCs). Using 2,2',7-,7'-tetrakis(N,N-di-p-methoxyphenyl-amine) 9,9'-spirobifuorene (Spiro-OMeTAD) as hole-transport material, a good conversion efficiency of 5.8% was recorded for cells based on the MKA16 dye and a high photovoltage of 840 mV in comparison with 5.6% efficiency using the known (Dyenamo Blue) dye. By co-sensitization using the orange-colored D35 dye and MKA16 together, the solid-state solar cells showed an excellent efficiency of 7.5%, with a high photocurrent of 12.41 mA cm(-2) and open-circuit voltage of 850 mV. The results show that the photocurrent of ssDSSCs can be significantly improved by co-sensitization mainly attributed to the wider light absorption range contributing to the photocurrent. In addition, results from photo-induced absorption spectroscopy show that the dye regeneration is efficient in co-sensitized solar cells. The current results possible routes of improving the design of aesthetic and highly efficient ssDSSCs.
A series of molecularly engineered and novel dyes WS1, WS2, WS3, and WS4, based on the D35 donor, 1-(4-hexylphenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole and 4-(4-hexylphenyl)-4H-dithieno[3,2-b: 2', 3'-d] pyrrole as pi-conjugating linkers, were synthesized and compared to the well-known LEG4 dye. The performance of the dyes was investigated in combination with an electrolyte based on Co(II/III) complexes as redox shuttles. The electron recombination between the redox mediators in the electrolyte and the TiO2 interface decreases upon the introduction of 4-hexylybenzene entities on the 2,5-di(thiophen-2-yl)-1H-pyrrole and 4H-dithieno[3,2-b: 2', 3'-d] pyrrole linker units, probably because of steric hindrance. The open circuit photovoltage of WS1-, WS2-, WS3-, and WS4-based devices in combination with the Co(II/III)-based electrolyte are consistently higher than those based on a I-/I-3(-) electrolyte by 105, 147, 167, and 75 mV, respectively. The WS3-based devices show the highest power conversion efficiency of 7.4% at AM 1.5 G 100 mW/cm(2) illumination mainly attributable to the high open-circuit voltage (V-OC).