The most commonly used redox mediators in dye-sensitized solar cells (DSCs), iodide/triiodide and cobalt trisbipyridine ([Co(bpy) 3 ] 2+/3+ ), were successfully replaced by bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) ([Cu-(dmp) 2 ] 1+/2+ ). The use of the copper complex based electrolyte led to an exceptionally high photovoltaic performance of 8.3% for LEG4-sensitized TiO 2 solar cells, with a remarkably high open-circuit potential of above 1.0 V at 1000 W m −2 under AM1.5G conditions. The copper complex based redox electrolyte has higher diffusion coefficients and is considerably faster in dye regeneration than comparable cobalt trisbipyridine based electrolytes. A driving force for dye regeneration of only 0.2 eV is sufficient to obtain unit yield, pointing to new possibilities for improvement in DSC efficiencies. The interaction of the excited dye with components of the electrolyte was monitored using steady-state emission measurements and time-correlated single-photon counting (TC-SPC). Our results indicate bimolecular reductive quenching of the excited LEG4 dye by the [Cu(dmp) 2 ] 2+ complex through a dynamic mechanism. Excited-state dye molecules can readily undergo bimolecular electron transfer with a suitable donor molecule. In DSCs this process can occur when the excited dye is unable to inject electrons into the TiO 2 . With a high electrolyte concentration the excited dye can be intercepted with an electron from the electrolyte resulting in the reduced state of the dye. Quenching of the reduced dye by the electrolyte competes with electron injection and results in a lower photocurrent. Quenching of excited LEG4 by complexes of [Cu(dmp) 2 ] + , [Co(bpy) 3 ] 2+ , and [Co(bpy) 3 ] 3+ followed a static mechanism, due ground-state dye−quencher binding. Inhibition of unwanted quenching processes by structural modifications may open ways to further increase the overall efficiency.
Through introducing an energy antenna system into a simple phenoxazine dye (TH301), a novel and efficient dye TH305 was designed and synthesized for application in a dye sensitized solar cell with prominent overall conversion efficiency of 7.7%.
A new strategy in which the anchoring group is separated from the acceptor groups of the dyes was developed; among these dyes, the HY103 dye gives a maximum IPCE value of 86% at 660 nm and an eta value of 3.7% in the NIR region reported in DSCs.
Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy—by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte—to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system.
Minimizing the driving force required for the regeneration of oxidized dyes using redox mediators in an electrolyte is essential to further improve the open-circuit voltage and efficiency of dye-sensitized solar cells (DSSCs). Appropriate combinations of redox mediators and dye molecules should be explored to achieve this goal. Herein, we present a triphenylamine dye, LEG4, in combination with a TEMPO-based electrolyte in acetonitrile (E(0) = 0.89 V vs. NHE), reaching an efficiency of up to 5.4% under one sun illumination and 40% performance improvement compared to the previously and widely used indoline dye D149. The origin of this improvement was found to be the increased dye regeneration efficiency of LEG4 using the TEMPO redox mediator, which regenerated more than 80% of the oxidized dye with a driving force of only ∼0.2 eV. Detailed mechanistic studies further revealed that in addition to electron recombination to oxidized dyes, recombination of electrons from the conducting substrate and the mesoporous TiO2 film to the TEMPO(+) redox species in the electrolyte accounts for the reduced short circuit current, compared to the state-of-the-art cobalt tris(bipyridine) electrolyte system. The diffusion length of the TEMPO-electrolyte based DSSCs was determined to be ∼0.5 μm, which is smaller than the ∼2.8 μm found for cobalt-electrolyte based DSSCs. These results show the advantages of using LEG4 as a sensitizer, compared to previously record indoline dyes, in combination with a TEMPO-based electrolyte. The low driving force for efficient dye regeneration presented by these results shows the potential to further improve the power conversion efficiency (PCE) of DSSCs by utilizing redox couples and dyes with a minimal need of driving force for high regeneration yields.
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