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Nickel-Based Two-Electron Redox Shuttle for Dye-Sensitized Solar Cells in Low Light Applications
Ravinder Kaur ; Niharika Dalpati ; Jared H. Delcamp , et al. ACS Appl. Energy Mater.,2024,7(9):3645-3655. DOI: 10.1021/acsaem.3c03198
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Abstract: Dye-sensitized solar cells (DSCs) are important to indoor solar powered devices and energy sustainable buildings because of their remarkable performance under indoor/ambient light conditions. Triiodide/iodide (I3–/I–) has been used as the most common redox mediator in DSCs because of its desirable kinetic properties and multielectron redox cycle. However, the low redox potential, corrosiveness, competitive visible light absorption, and lack of tunability of this redox mediator limit its performance in many DSC devices. Here we report a class of transition metal complex redox shuttles which operate on a similar multielectron redox cycle as I3–/I– while maintaining desirable kinetics and improving on its limitations. These complexes, nickel dithiocarbamates, were evaluated as redox shuttles in DSCs, which exhibited excellent performance under low light conditions. The recombination behavior of the redox shuttles with electrons in TiO2, dye regeneration behavior, and counter electrode electron transfer resistance were studied via chronoamperometry and electrochemical impedance spectroscopy (EIS). Further, DSC devices were studied with the Ni-based redox shuttles via incident photon-to-current conversion efficiencies (IPCEs) and current–voltage (J–V) curves under varied light intensities. The Ni-based redox shuttles showed up to 20.4% power conversion efficiency under fluorescent illumination, which was higher than I3–/I–-based devices (13%) at similar electrolyte concentrations. Taken together, these results show that nickel dithiocarbamate redox shuttles have faster rates of dye regeneration than the I3–/I– shuttle but suffer from faster recombination of photoinjected electrons with oxidized Ni(IV) species, which decrease photovoltages.
Keywords: dye-sensitized solar cells ; nickel(IV) ; redox shuttle ; dithiocarbamate ; indoor photovoltaic
Purchased from AmBeed: 3978-81-2 ; 90076-65-6
CAS No. : | 90076-65-6 | MDL No. : | MFCD00210017 |
Formula : | C2F6LiNO4S2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | QSZMZKBZAYQGRS-UHFFFAOYSA-N |
M.W : | 287.09 | Pubchem ID : | 3816071 |
Synonyms : |
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Signal Word: | Danger | Class: | 8,6.1 |
Precautionary Statements: | P260-P264-P270-P273-P280-P301+P310+P330-P301+P330+P331-P303+P361+P353-P304+P340+P310-P305+P351+P338+P310-P314-P361+P364-P405-P501 | UN#: | 2923 |
Hazard Statements: | H301+H311-H314-H372-H412 | Packing Group: | Ⅱ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
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62% | In acetonitrile; at 20℃; for 48h; | The ionic liquid EMI?TFSI- was synthesized by a one step methathesis: 1-ethyl-3-methylimidazoliumchloride EMI?Cl- (1.465 g, 0.01 mol) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (2.871 g, 0.01 mol) were dissolved in acetonitrile intwo separate vials. An anion-exchange reaction occurred after adding slowly (drop bydrop) LiTFSI solution in a 10 mL round-bottom flask containing the EMI?Cl- solution,whereby the mixture was precipitated. Then, the reaction mixture was stirred at 500 rpm atroom temperature for 48 h. After removal of the solvent, the mixture was washedrepeatedly with water until the Cl- could not be detected by addition of AgNO3 solution.The organic phase was collected in a vial and was passed at least twice through Celitesilica column with ethyl acetate to completely remove Cl-. After removal of the solvent,the final product was dried under vacuum to give a yellowish liquid (2.347 g, 62 %). |
Yield | Reaction Conditions | Operation in experiment |
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In dichloromethane; water; at 20.0℃; for 24.0h; | General procedure: A dried 250 ml round bottom flask was prepared, and 50 ml of DCM (dichloromethane) was added to 1-(Trimethylsilyl)methyl-1-methylpyrrolidinium chloride (10 g, 0.05 mol) and stirred at room temperature.Lithium bis(fluorosulfonyl)imide (9.2 g, 0.05 mol) and 50 ml of DIW (distilled water) were dissolved in a dropping funnel and added dropwise over 10 minutes.After completion of dropwise addition, the reaction was stirred at room temperature for 24 hours.After completion of the reaction, the organic layer is separated using a separator funnel,The organic layer was washed with 50 ml of DIW. The organic layer was added with MgSO4 and filtered, The solvent was removed by distillation and distillation under vacuum to obtain the desired product, 1-(Trimethylsilyl)methyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (15g, yield = 90%). |