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Supporting Information for: A New Direction in Dye-Sensitized Solar Cells Redox Mediator Development: In-Situ Fine-Tuning of the Cobalt(II)/(III) Redox Potential through Lewis Base Interactions
Muhammad K. Kashifa, Jordan C. Axelsonb, Noel Duffyc, Craig M. Forsythd, Christopher J. Change, Jeffrey R. Longb, Leone Spiccia*d and Udo Bach*a,f,g
KEYWORDS. Dye-sensitized solar cell, redox mediators, cobalt(II)/(III) pentapyridyl complexes, Lewis base interactions, tuning redox potentials
Commonwealth Scientific and Industrial Research Organization, Energy Technology, Clayton South, Victoria 3169, Australia
d
Department of Chemistry and the Howard Hughes Medical Institute, University of California, Berkeley, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, United States
f
Commonwealth Scientific and Industrial Research Organization, Materials Science and Engineering, Clayton South, Victoria 3169, Australia
g
Melbourne Centre for Nanofabrication, 151 Wellington Road, Clayton, Victoria 3168, Australia
Figure S1: Cyclic voltammogram of [Co(PY5Me2)(MeCN)](OTf)2 (1a), [Co(PY5Me2)(tBP)](OTf)2 (2a), [Co(PY5Me2)(NMBI)](OTf)2 (3a) measured using a 10 mM solution in MeCN on a glassy carbon disk electrode and 100 mM (Bu4N)PF6 as supporting electrolyte at a scan rate of 100 mV/sec.
Figure S2: UV-Vis spectra of 2a, 2b, 3a and 3b measured for a 5 mM MeCN solutions of each complex (1 cm path length cuvette).
Figure S3. Top view of [Co(PY5Me2)(tBP)]2+ (2a cation) and [Co(PY5Me2)(NMBI)]2+ cations (3a cation) with pale blue, grey and dark blue spheres representing Co, C, and N respectively. The O3SCF3 anions and solvent MeCN molecules have been omitted for clarity. The complexes are highly symmetrical along the PY1-Me2 and axial ligand (tBP and NMBI) axis.
Figure S4. View of the [Co(PY5Me2)(NMBI)]2+ cation of [Co(PY5Me2)(NMBI)](TFSI)33(CH2Cl2) (3b) with non-hydrogen atoms represented by 50% thermal ellipsoids and hydrogen atoms as spheres of arbitrary size; the counter anions and lattice solvent molecules have been omitted for clarity.
Table S1. Tabulated photovoltaic performance data of devices made with the redox couple 3a/b and the MK2 dye. All the devices are measured at given simulated sunlight intensities. Electrolyteb 3a/3b
a
Intensity 100 40 10
Double-layer TiO2 films (1 m mesoporous TiO2 (30 nm) and 2 m scattering TiO2 (400 nm)) were used for the construction of all DSCs. 0.5 m thick PEDOT was used as counter electrode, which was grown electrochemically on FTO using a 20 mM solution of EDOT monomer in acetonitrile and 100 mM LiTFSI as supporting electrolyte. IV characteristic data is averaged for three DSCs. bThe electrolyte consists of CoII, 0.2 M, CoIII 0.75 M, lithium trifluoromethanesulfonimide (LiTFSI) 0.1 M.
Figure S5: Photocurrent dynamics during a 2.5 sec on-stage under simulated sunlight (AM 1.5G, 1,000 W/cm2).
Figure S6. Extracted charge per film area vs open circuit voltage. Measured by IMVS and charge extraction method for MK2-sensitized DSCs. The devices were constructed using 2 m thick mesoporous TiO2 (30 nm) films and filled with corresponding redox shuttle (explained in graph). The electrolyte concentration was consistent as explained in the Table 2. The average diffusion length (Ln) was estimated to be 3.4 m from [Tn Dn]1/2, so it is expected that the charge collection at short circuit is efficient.