Rational screening low-cost counter electrodes for dye-sensitized solar cells

Dye-sensitized solar cells have attracted intense research attention owing to their ease of fabrication, cost-effectiveness and high efficiency in converting solar energy. Noble platinum is generally used as catalytic counter electrode for redox mediators in electrolyte solution. Unfortunately, platinum is expensive and non-sustainable for long-term applications. Therefore, researchers are facing with the challenge of developing low-cost and earth-abundant alternatives. So far, rational screening of non-platinum counter electrodes has been hamstrung by the lack of understanding about the electrocatalytic process of redox mediators on various counter electrodes. Here, using first-principle quantum chemical calculations, we studied the electrocatalytic process of redox mediators and predicted electrocatalytic activity of potential semiconductor counter electrodes. On the basis of theoretical predictions, we successfully used rust (alpha-Fe2O3) as a new counter electrode catalyst, which demonstrates promising electrocatalytic activity towards triiodide reduction at a rate comparable to platinum.

Highly Electrocatalytic Activity of RuO2 Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSCs) are promising alternatives to conventional silicon devices because of their simple fabrication procedure, low cost, and high efficiency. Platinum is generally used as a superior counter electrode (CE) material, but the disadvantages such as high cost and low abundance greatly restrict the large-scale application of DSCs. An efficient and sustainable way to overcome the limited supply of Pt is the development of high-efficiency Pt-free CE materials, which should possess both high electrical conductivity and superior electrocatalytic activity simultaneously. Herein, for the first time, a two-step strategy to synthesize ruthenium dioxide (RuO2) nanocrystals is reported, and it is shown that RuO2 catalysts exhibit promising electrocatalytic activity towards triiodide reduction, which results in comparable energy conversion efficiency to that of conventional Pt CEs. More importantly, by virtue of first-principles calculations, the catalytic mechanism of electrocatalysis for triiodide reduction on various CEs is investigated systematically and it is found that the electrochemical triiodide reduction reaction on RuO2 catalyst surfaces can be enhanced significantly, owing to the ideal combination of good electrocatalytic activity and high electrical conductivity.

Facet-Dependent Catalytic Activity of Platinum Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells

Platinum (Pt) nanocrystals have demonstrated to be an effective catalyst in many heterogeneous catalytic processes. However, pioneer facets with highest activity have been reported differently for various reaction systems. Although Pt has been the most important counter electrode material for dye-sensitized solar cells (DSCs), suitable atomic arrangement on the exposed crystal facet of Pt for triiodide reduction is still inexplicable. Using density functional theory, we have investigated the catalytic reaction processes of triiodide reduction over {100}, {111} and {411} facets, indicating that the activity follows the order of Pt(111) > Pt(411) > Pt(100). Further, Pt nanocrystals mainly bounded by {100}, {111} and {411} facets were synthesized and used as counter electrode materials for DSCs. The highest photovoltaic conversion efficiency of Pt(111) in DSCs confirms the predictions of the theoretical study. These findings have deepened the understanding of the mechanism of triiodide reduction at Pt surfaces and further screened the best facet for DSCs successfully.

Dual interfacial modifications of hierarchically structured iodine-doped ZnO photoanodes for high-efficiency dye-sensitized solar cells

A nanocomposite porous electrode structure consisting of hierarchical iodine-doped zinc oxide (I-ZnO) aggregates combined with the two simple solution-processed interfacial modifications i.e. a ZnO compact layer (CL) and a TiO2 protective layer (PL) has been developed in order to understand electron transport and recombination in the photoanode matrix, together with boosting the conversion efficiency of I-ZnO based dye-sensitized solar cells (DSCs). Electrochemical impedance spectra demonstrate that ZnO CL pre-treatment and TiO2 PL post-treatment synergistically reduce charge-transfer resistance and suppress electron recombination. Furthermore, the electron lifetime in two combined modifications of IZnO + CL + PL photoelectrode is the longest in comparison with the other three photoelectrodes. As a consequence, the overall conversion efficiency of I-ZnO + CL + PL DSC is significantly enhanced to 6.79%, with a 36% enhancement compared with unmodified I-ZnO DSC. Moreover, the stability of I-ZnO + CL + PL cell is improved as compared to I-ZnO one. The mechanism of electron transfer and recombination upon the introduction of ZnO CL and TiO2 PL is also proposed in this work.

Dye-sensitized solar cells based on perylene derivatives

The oil price rises more and more, and the world energy consumption is projected to expand by 50 percent from 2005 to 2030. Nowadays intensive research is focused on the development of alternative energies. Among them, there are dye-sensitized nanocrystalline solar cells (DSSCs) “the third generation solar cells”. The latter have gained attention during the last decade and are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic. At present DSSCs with ruthenium based dyes exhibit highest efficiencies (ca 11%). The objective of the present work is to fabricate, characterize and improve the performance of DSSCs based on metal free dyes as sensitizers, especially on perylene derivatives. The work begins by a general introduction to the photovoltaics and dye-sensitized solar cells, such as the operating principles and the characteristics of the DSSCs. Chapter 2 and 3 discuss the state of the art of sensitizers used in DSSCs, present the compounds used as sensitizer in the present work and illustrate practical issues of experimental techniques and device preparation. A comparative study of electrolyte-DSSCs based on P1, P4, P7, P8, P9, and P10 are presented in chapter 4. Experimental results show that the dye structure plays a crucial role in the performance of the devices. The dye based on the spiro-concept (bipolar spiro compound) exhibited a higher efficiency than the non-spiro compounds. The presence of tert-butylpyridine as additive in the electrolyte was found to increase the open circuit voltage and simultaneously decrease the efficiency. The presence of lithium ions in the electrolyte increases both output current and the efficiency. The sensitivity of the dye to cations contained in the electrolyte was investigated in the chapter 5. FT-IR and UV-Vis were used to investigate the in-situ coordination of the cation to the adsorbed dye in the working devices. The open-circuit voltage was found to depend on the number of coordination sites in the dye. P1 with most coordination sites has shown the lowest potential drop, opposite to P7, which is less sensitive to cations in the working cells. A strategy to improve the dye adsorption onto the TiO2 surface, and thus the light harvesting efficiency of the photoanode by UV treatment, is presented in chapter 6. The treatment of the TiO2 film with UV light generates hydroxyl groups and renders the TiO2 surface more and more hydrophilic. The treated TiO2 surface reacts readily with the acid anhydride group of the dye that acts as an anchoring group and improves the dye adsorption. The short-circuit current density and the efficiency of the electrolyte-based dye cells was considerably improved by the UV treatment of the TiO2 film. Solid-state dye-sensitized solar cells (SSDs) based on spiro-MeOTAD (used as hole transport material) are studied in chapter 7. The efficiency of SSDs was globally found to be lower than that of electrolyte-based solar cells. That was due to poor pore filling of the dye-loaded TiO2 film by the spin-coated spiro-MeOTAD and to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator. However, the presence of the donor moieties in P1 that are structurally similar to spiro-MeOTAD was found to improve the wettability of the P1-loaded TiO2 film. As a consequence the performance of the P1-based solid-state cells is better compared to the cells based on non-spiro compounds.

Role of Polyelectrolyte for Layer-by-Layer Compact TiO(2) Films in Efficiency Enhanced Dye-Sensitized Solar Cells

Efficient compact TiO(2) films using different polyeleetrolytes are prepared by the layer-by-layer technique (LbL) and applied as an effective contact and blocking film in dye-sensitized solar cells (DSCs). The polyanion thermal stability plays a major role on the compact layers, which decreases back electron transfer processes and current losses at the FTO/TiO(2) interface. FESEM images show that polyelectrolytes such is sodium sullonated polystyrene (PSS) and sulfonated lignin (SE), in comparison to poly(acrylic acid) (FAA), ensure an adequate morphology for the LbL TiO(2) layer deposited before the mesoporous film, even triter the sintering step at 450 degrees C. The so treated photoanode in DSCs leads to a 30% improvement On the overall conversion efficiency. Electrochemical impedance spectroscopy (EIS) is employed to ascertain the role of die compact films with such polyelectrolytes. The significant increase in V(oc) of the solar cells with adequate polyelectrolytes in the LbL TiO(2) films shows their pivotal role in decreasing the electron recombination at the FTO surface and enhancing the electrical contact of FTO with the mesoporous TiO(2) layer.

Layer-by-layer TiO(2) films as efficient blocking layers in dye-sensitized solar cells

Charge recombination at the conductor substrate/electrolyte interface has been prevented by using efficient blocking layers of TiO(2) compact films in dye-sensitized solar cell photoanodes. Compact blocking layers have been deposited before the mesoporous TiO(2) film by the layer-by-layer technique using titania nanoparticles as cations and sodium sulfonated polystyrene, PSS, as a polyanion. The TiO(2)/PSS blocking layer in a DSC prevents the physical contact of FTO and the electrolyte and leads to a 28% increase in the cell`s overall conversion efficiency, from 5.7% to 7.3%. (C) 2009 Elsevier B.V. All rights reserved.

Efficient and low cost devices for solar energy conversion: Efficiency and stability of some natural-dye-sensitized solar cells

Dye-sensitized solar cells, named by us Dye-Cells, are one of the most promising devices for solar energy conversion due to their reduced production cost and low environmental impact, especially those sensitized by natural dyes. The efficiency and stability of devices based on natural sensitizers such as mulberry (Morus alba Lam), blueberry (Vaccinium myrtillus Lam), and jaboticaba`s skin (Mirtus cauliflora Mart) were investigated. Dye-Cells prepared with aqueous mulberry extract presented the highest P(max) value (1.6 mW cm(-2)) with J(sc) = 6.14 mA cm(-2) and V(oc) = 0.49 V, Photoelectrochemical parameters of 16 cm(2) active area devices sensitized by mulberry dye were constant for 14 weeks of continuous evaluation. Moreover, the cell remained stable even after 36 weeks with a fairly good efficiency. Therefore, mulberry dye opens up a perspective of commercial feasibility for inexpensive and environmentally friendly Dye-Cells. (C) 2009 Elsevier B.V. All rights reserved.

Impedance Spectroscopy Analysis of the Effect of TiO2 Blocking Layers on the Efficiency of Dye Sensitized Solar Cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Doping saturation in dye-sensitized solar cells based on ZnO:Ga nanostructured photoanodes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electron Transport in Dye-Sensitized Solar Cells Based on ZnO Nanotubes: Evidence for Highly Efficient Charge Collection and Exceptionally Rapid Dynamics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis and characterization of ZnO and ZnO : Ga films and their application in dye-sensitized solar cells

Highly crystalline ZnO and Ga-modified zinc oxide (ZnO:Ga) nanoparticles containing 1, 3 and 5 atom% of Ga3+ were prepared by precipitation method at low temperature. The films were characterized by XRD, BET, XPS and SEM. No evidence of zinc gallate formation (ZnGa2O4), even in the samples containing 5 atom% of gallium, was detected by XRD. XPS data revealed that Ga is present into the ZnO matrix as Ga3+, according to the characteristic binding energies. The particle size decreased as the gallium level was increased as observed by SEM, which might be related to a faster hydrolysis reaction rate. The smaller particle size provided films with higher porosity and surface area, enabling a higher dye loading. When these films were applied to dye-sensitized solar cells (DSSCs) as photoelectrodes, the device based on ZnO: Ga 5 atom% presented an overall conversion efficiency of 6% (at 10 mW cm(-2)), a three-fold increase compared to the ZnO-based DSSCs under the same conditions. To our knowledge, this is one of the highest efficiencies reported so far for ZnO-based DSSCs. Transient absorption (TAS) study of the photoinduced dynamics of dye-sensitized ZnO:Ga films showed that the higher the gallium content, the higher the amount of dye cation formed, while no significant change on the recombination dynamics was observed. The study indicates that Ga-modification of nanocrystalline ZnO leads to an improvement of photocurrent and overall efficiency in the corresponding device.

Efficient Dye-Sensitized Solar Cells Based on the Combination of ZnO Nanorods and Microflowers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ga-Modified Nanostructured ZnO: Characterization and Application in Dye-Sensitized Solar Cells

ZnO has received great attention in many applications due to its electronic and optical properties. We report on the preparation of ZnO and gallium-containing ZnO (ZnO:Ga) nanoparticles by the precipitation method. The nanoparticles have the wurtzite structure and a high crystallinity. Gallium ions are present as Ga(3+), as evidenced by the binding energies through XPS. Porosity and surface area of the powder increased under increasing gallium level, explained by the smaller particle size of ZnO:Ga samples compared with ZnO. The estimated optical band gap of ZnO was 3.2 eV, comparable to ZnO:Ga.