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| 2. |
- Benesperi, Iacopo, et al.
(författare)
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Dynamic dimer copper coordination redox shuttles
- 2022
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Ingår i: Chem. - : Elsevier. - 2451-9308 .- 2451-9294. ; 8:2, s. 439-449
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Tidskriftsartikel (refereegranskat)abstract
- Summary Conventional redox mediators based on metal coordination complexes undergo electron transfer through the change in oxidation state of the metal center. However, electron transfer kinetics are offset toward preferred oxidation states when preorganized ligands constrain the reorganization of the coordination sphere. In contrast, we report here on dimeric copper(II/I) redox couples, wherein the extent of oxidation/reduction of two metal centers dictates the dynamic formation of dimer and monomer complexes: the dimeric (Cu(I))2 transitions to monomers of Cu(II). The bis(thiazole/pyrrole)-bipyridine tetradentate ligands stabilize both oxidation states of the unique redox systems. The dynamic dimer redox mediators offer a viable two-electron redox mechanism to develop efficient hybrid solar cells through inhibited recombination and rapid charge transport. Density functional theory calculations reveal inner reorganization energies for single-electron transfer as low as 0.27 eV, marking the dimeric complexes superior redox systems over single complexes as liquid and potentially solid-state electrolytes.
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| 3. |
- Michaels, Hannes, et al.
(författare)
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Copper Complexes with Tetradentate Ligands for Enhanced Charge Transport in Dye-Sensitized Solar Cells
- 2018
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Ingår i: Inorganics. - : MDPI AG. - 2304-6740. ; 6:2
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Tidskriftsartikel (refereegranskat)abstract
- In dye-sensitized solar cells (DSCs), the redox mediator is responsible for the regeneration of the oxidized dye and for the hole transport towards the cathode. Here, we introduce new copper complexes with tetradentate 6,6-bis(4-(S)-isopropyl-2-oxazolinyl)-2,2-bipyridine ligands, Cu(oxabpy), as redox mediators. Copper coordination complexes with a square-planar geometry show low reorganization energies and thus introduce smaller losses in photovoltage. Slow recombination kinetics of excited electrons between the TiO2 and Cu-II(oxabpy) species lead to an exceptionally long electron lifetime, a high Fermi level in the TiO2, and a high photovoltage of 920 mV with photocurrents of 10 mA.cm(-2) and 6.2% power conversion efficiency. Meanwhile, a large driving force remains for the dye regeneration of the Y123 dye with high efficiencies. The square-planar Cu(oxabpy) complexes yield viscous gel-like solutions. The unique charge transport characteristics are attributed to a superposition of diffusion and electronic conduction. An enhancement in charge transport performance of 70% despite the higher viscosity is observed upon comparison of Cu(oxabpy) to the previously reported Cu(tmby)(2) redox electrolyte.
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| 4. |
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| 5. |
- Munoz-Garcia, Ana Belen, et al.
(författare)
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Dye-sensitized solar cells strike back
- 2021
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Ingår i: Chemical Society Reviews. - : Royal Society of Chemistry. - 0306-0012 .- 1460-4744. ; 50:22, s. 12450-12550
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Forskningsöversikt (refereegranskat)abstract
- Dye-sensitized solar cells (DSCs) are celebrating their 30th birthday and they are attracting a wealth of research efforts aimed at unleashing their full potential. In recent years, DSCs and dye-sensitized photoelectrochemical cells (DSPECs) have experienced a renaissance as the best technology for several niche applications that take advantage of DSCs' unique combination of properties: at low cost, they are composed of non-toxic materials, are colorful, transparent, and very efficient in low light conditions. This review summarizes the advancements in the field over the last decade, encompassing all aspects of the DSC technology: theoretical studies, characterization techniques, materials, applications as solar cells and as drivers for the synthesis of solar fuels, and commercialization efforts from various companies.
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| 6. |
- Munoz-Garcia, Ana Belen, et al.
(författare)
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Structural evolution of disordered LiCo(1/3)Fe(1/3)Mn(1/3)PO(4)in lithium batteries uncovered
- 2020
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7496 .- 2050-7488. ; 8:37, s. 19641-19653
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Tidskriftsartikel (refereegranskat)abstract
- In this study we address the Li-ion de-insertion/insertion mechanisms from/into the lattice of the mixed olivine LiCo1/3Fe1/3Mn1/3PO4(LCFMP). This mechanism is driven by a subtle interplay of structural, electronic and thermodynamic features. We aim at dissecting this complex landscape that is tightly connected to the long-term electrochemical performance of this material as a positive electrode in lithium-ion cells. To this end, we report advanced structural characterization, based onex situsynchrotronradiation diffraction on samples at different lithium contents. We couple this analysis with first-principles simulations, for a directvis-a-viscomparison. Our results show that (1) the mixing of the three transition-metal (TM) cations in the olivine lattice leads to a solid solution, providing the olivine lattice with the necessary flexibility to retain its single-phase structure during cell operation; (2) the electronic features of the three TMs are responsible for the observed electrochemical performance; (3) the de-lithiation of the olivine lattice is a thermodynamically driven process. Last but not least, our integrated experimental and theoretical results reveal the subtle features behind the formation of antisite defects that selectively involve Li-Co couples. In conclusion, our study provides the necessary scientific foundations to understand the structure-property-function relationships in LCFMP olivines, paving the way for further development and optimization of this material for application in Li-ion batteries.
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| 7. |
- Saygili, Yasemin, et al.
(författare)
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Copper Bipyridyl Redox Mediators for Dye-Sensitized Solar Cells with High Photovoltage
- 2016
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 138:45, s. 15087-15096
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Tidskriftsartikel (refereegranskat)abstract
- 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 TiO2 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)TFSI2/1 (0.97 V vs SHE, dmby = 6,6'-dimethyl-2,2'-bipyridine) and Cu-(II/I)(tmby)(2)TFSI2/1 (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)TFSI2/1 (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 mu s) was observed for both complexes. As another advantage, the electron back transfer (recombination) rates were slower with Cu-(II/I)(tmby)(2)TFSI2/1 as evidenced by longer lifetimes. The solar-to-electrical power conversion efficiencies for [Cu(tmby)(2)](2+/1+), [Cu(dmby)(2)](2+/1+) , and [Cu(dmp)(2)](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.
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| 8. |
- Saygili, Yasemin, et al.
(författare)
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Effect of Coordination Sphere Geometry of Copper Redox Mediators on Regeneration and Recombination Behavior in Dye-Sensitized Solar Cell Applications
- 2018
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Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 1:9, s. 4950-4962
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Tidskriftsartikel (refereegranskat)abstract
- 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, lambda, of tetra-coordinated Cu(I) species (lambda = 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 (lambda = 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 TiO2 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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| 9. |
- Spinelli, Giovanni, et al.
(författare)
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Conductivity in Thin Films of Transition Metal Coordination Complexes
- 2023
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Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 6:4, s. 2122-2127
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Tidskriftsartikel (refereegranskat)abstract
- Two coordination complexes have been made by combining the dithiolene complexes [M(mnt)(2)](2-) (mnt = maleonitriledithiolate; M = Ni2+ or Cu2+) as anion, with the copper(II) coordination complex [Cu(Stetra)] (Stetra = 6,6 ' - bis(4,5-dihydrothiazol-2-yl)-2,2 ' -bipyri-dine) as cation. The variation of the metal centers leads to a dramatic change in the conductivity of the materials, with the M = Cu2+ variant (Cu-Cu) displaying semiconductor behavior with a conductivity of approximately 2.5 x 10(-8) S cm(-1), while the M = Ni2+ variant (Ni-Cu) displayed no observable conductivity. Computational studies found Cu-Cu enables a minimization of reorganization energy losses and, as a result, a lower barrier to the charge transfer process, resulting in the reported higher conductivity.
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