Redox mediators play a major role determining the photocurrent and the photovoltage in dye-sensitized solar cells (DSCs). To maintain the photocurrent, the reduction of oxidized dye by the redox mediator should be significantly faster than the electron back transfer between TiO 2 and the oxidized dye. The driving force for dye regeneration with the redox mediator should be sufficiently low to provide high photovoltages. With the introduction of our new copper complexes as promising redox mediators in DSCs both criteria are satisfied to enhance power conversion efficiencies. In this study, two copper bipyridyl complexes, Cu (II/I) (dmby) 2 TFSI 2/1 (0.97 V vs SHE, dmby = 6,6′-dimethyl-2,2′-bipyridine) and Cu (II/I) (tmby) 2 TFSI 2/1 (0.87 V vs SHE, tmby = 4,4′,6,6′-tetramethyl-2,2′-bipyridine), are presented as new redox couples for DSCs. They are compared to previously reported Cu (II/I) (dmp) 2 TFSI 2/1 (0.93 V vs SHE, dmp = bis(2,9-dimethyl-1,10-phenanthroline). Due to the small reorganization energy between Cu(I) and Cu(II) species, these copper complexes can sufficiently regenerate the oxidized dye molecules with close to unity yield at driving force potentials as low as 0.1 V. The high photovoltages of over 1.0 V were achieved by the series of copper complex based redox mediators without compromising photocurrent densities. Despite the small driving forces for dye regeneration, fast and efficient dye regeneration (2−3 μs) was observed for both complexes. As another advantage, the electron back transfer (recombination) rates were slower with Cu (II/I) (tmby) 2 TFSI 2/1 as evidenced by longer lifetimes. The solar-toelectrical power conversion efficiencies for [Cu(tmby) 2+/1+ based electrolytes were 10.3%, 10.0%, and 10.3%, respectively, using the organic Y123 dye under 1000 W m −2 AM1.5G illumination. The high photovoltaic performance of Cu-based redox mediators underlines the significant potential of the new redox mediators and points to a new research and development direction for DSCs.
Solid-state dye-sensitized solar cells currently suffer from issues such as inadequate nanopore filling, low conductivity and crystallization of hole-transport materials infiltrated in the mesoscopic TiO2 scaffolds, leading to low performances. Here we report a record 11% stable solid-state dye-sensitized solar cell under standard air mass 1.5 global using a hole-transport material composed of a blend of [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)2](bis(trifluoromethylsulfonyl)imide)2 and [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)2](bis(trifluoromethylsulfonyl)imide). The amorphous Cu(II/I) conductors that conduct holes by rapid hopping infiltrated in a 6.5 μm-thick mesoscopic TiO2 scaffold are crucial for achieving such high efficiency. Using time-resolved laser photolysis, we determine the time constants for electron injection from the photoexcited sensitizers Y123 into the TiO2 and regeneration of the Y123 by Cu(I) to be 25 ps and 3.2 μs, respectively. Our work will foster the development of low-cost solid-state photovoltaic based on transition metal complexes as hole conductors.
The relatively large voltage loss (V loss ) in excitonic type solar cells severely limits their power conversion efficiencies (PCEs). Here, we report a comprehensive control of V loss through efficacious engineering of the sensitizer and redox mediator, making a breakthrough in the PCE of dye-sensitized solar cells (DSSCs).The targeted down-regulation of V loss is successfully realized by three valid channels: (i) reducing the driving force of electron injection through dye molecular engineering, (ii) decreasing the dye regeneration overpotential through redox mediator engineering, and (iii) suppressing interfacial electron recombination.Significantly, the ''trade-off'' effect between the dye optical band gap and the open-circuit voltage (V OC ) is minimized to a great extent, achieving a distinct enhancement in photovoltaic performance (PCE 4 11.5%with V OC up to 1.1 V) for liquid junction cells. The solidification of the best-performing device leads to a PCE of 11.7%, which is so far the highest efficiency obtained for solid-state DSSCs. Our work inspires further development in highly efficient excitonic solar cells by comprehensive control of V loss . Broader contextExcitonic type solar cells, including dye-sensitized solar cells (DSSCs), perovskite solar cells (PSCs) and organic solar cells (OSCs), are potential alternatives for photovoltaic applications. To further advance their power conversion efficiencies (PCEs), it is crucial to reduce the so called voltage loss (V loss ) as much as possible. In DSSCs, the V loss mainly takes place in the electron injection, dye regeneration and interfacial recombination processes, whereas the targeted decreasing of V loss in all these aspects has been rarely reported. To address this issue, we herein demonstrate a comprehensive control of V loss , achieving 11.7% efficiency for solid-state DSSCs. This work is a good example of radically improving the PCE through rationally reducing V loss .
Three Cu(II/I)-phenanthroline and Cu(II/I)-bipyridine redox mediators are studied on various electrodes and in variety of electrolyte solutions using cyclic voltammetry and impedance spectroscopy on symmetrical dummy cells. Graphene-based catalysts provide comparably high activity to PEDOT, and both catalysts outperform the activity of platinum. The chargetransfer kinetics and the diffusion rate significantly slowdown in the presence 4-tertbutylpyridine. This effect is specific only for Cu-mediators (is missing for Co-mediators), and is ascribed to a sensitivity of the coordination sphere of the Cu(II)-species to structural and substitutional changes. The 'Zombie Cells' made from symmetrical PEDOT/PEDOT devices exhibit enhanced charge-transfer rate and enhanced diffusion resistance. Electrochemically clean Cu(II)-bipyridine species are prepared, for the first time, by electrochemical oxidation of the parent Cu(I) complexes. Our preparative electrolysis brings numerous advantages over the standard chemical syntheses of the Cu(II)-bipyridine complexes. The superior performance of electrochemically-grown clean Cu(II)-bipyridine complex is demonstrated on practical dye-sensitized solar cells.
Rapid extraction of photogenerated charge carriers is essential to achieve high efficiencies with perovskite solar cells (PSCs). Here, a new mesoscopic architecture as electron‐selective contact for PSCs featuring 40 nm sized TiO2 beads endowed with mesopores of a few nanometer diameters is introduced. The bimodal pore distribution inherent to these films produces a very large contact area of 200 m2 g−1 whose access by the perovskite light absorber is facilitated by the interstitial voids between the particles. Modification of the TiO2 surface by CsBr further strengthens its interaction with the perovskite. As a result, photogenerated electrons are extracted rapidly producing a very high fill factor of close to 80% a VOC of 1.14 V and a PCE up to 21% with negligible hysteresis.
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.
The recombination of injected electrons with oxidized redox species and regeneration behavior of copper redox mediators are investigated for four copper complexes, [Cu(dmby) 2 ] 2+/1+ (dmby = 6,6′-dimethyl-2,2′bipyridine), [Cu(tmby) 2 ] 2+/1+ (tmby = 4,4′,6,6′-tetramethyl-2,2′-bipyridine), [Cu(eto) 2 ] 2+/1+ (eto = 4-ethoxy-6,6′-dimethyl-2,2′-bipyridine), and [Cu-(dmp) 2 ] 2+/1+ (dmp = bis(2,9-dimethyl-1,10-phenantroline). These complexes were examined in conjunction with the D5, D35, and D45 sensitizers, having various degrees of blocking moieties. The experimental results were further supported by density functional theory calculations, showing that the low reorganization energies, λ, of tetra-coordinated Cu(I) species (λ = 0.31−0.34 eV) allow efficient regeneration of the oxidized dye at driving forces down to approximately 0.1 eV. The regeneration electron transfer reaction is in the Marcus normal regime. However, for Cu(II) species, the presence of 4-tertbutylpyridine (TBP) in electrolyte medium results in penta-coordinated complexes with altered charge recombination kinetics (λ = 1.23−1.40 eV). These higher reorganization energies lead to charge recombination in the Marcus normal regime instead of the Marcus inverted regime that could have been expected from the large driving force for electrons in the conduction band of TiO 2 to react with Cu(II). Nevertheless, the recombination resistance and electron lifetime values were higher for the copper redox species compared to the reference cobalt redox mediator. The DSC devices employing D35 dye with [Cu(dmp) 2 ] 2+/1+ reached a record value for the open circuit voltage of 1.14 V without compromising the short circuit current density value. Even with the D5 dye, which lacks recombination preventing steric units, we reached 7.5% efficiency by employing [Cu(dmp) 2 ] 2+/1+ and [Cu(dmby) 2 ] 2+/1+ at AM 1.5G full sun illumination with open circuit voltage values as high as 1.13 V.
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