Liquid crystal (LC; E7 and/or ML-0249)-embedded, poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based, polymer electrolytes were prepared for use in dye-sensitized solar cells (DSSCs). The electrolytes contained 1-methyl-3-propylimidazolium iodide (PMII), tetrabutylammonium iodide (TBAI), and iodine (I 2 ), which participate in the I 3 -/I -redox couple. The incorporation of photochemically stable PVdF-co-HFP in the DSSCs created a stable polymer electrolyte that resisted leakage and volatilization. DSSCs, with liquid crystal (LC)-embedded PVdF-co-HFP-based polymer electrolytes between the amphiphilic ruthenium dye N719 absorbed to the nanocrystalline TiO 2 photoanode and the Pt counter electrode, were fabricated. These DSSCs displayed enhanced redox couple reduction and reduced charge recombination in comparison to that fabricated from the conventional PVdF-co-HFP-based polymer electrolyte. The behavior of the polymer electrolyte was improved by the addition of optimized amounts of plasticizers, such as ethylene carbonate (EC) and propylene carbonate (PC). The significantly increased short-circuit current density (J s c , 14.60 mA/cm 2 ) and open-circuit voltage (V o c, 0.68 V) of these DSSCs led to a high power conversion efficiency (PCE) of 6.42% and a fill factor of 0.65 under a standard light intensity of 100 mW/cm 2 irradiation of AM 1.5 sunlight. A DSSC fabricated by using E7-embedded PVdF-co-HFP-based polymer electrolyte exhibited a maximum incident photon-to-current conversion efficiency (IPCE) of 50%.
The polymerization of a cyclopolymerizable disubstituted dipropargyl ether, bis(3-trimethylsilyl-2-propynyl)ether (BTPE), was attempted by various transition metal catalysts. The yield for the polymerization of BTPE was generally low, which is possibly due to the steric hindrance of bulky substituents. In general, the catalytic activities of Mo-based catalysts were found to be greater than those of W-based catalysts. The highest yield was obtained when the MoCl 5 -EtAlCl 2 (1 : 2) catalyst system was used. The copolymerization of BTPE and diethyl dipropargylmalonate yielded a random copolymer with conjugated polymer backbone. However the polymers were partially desilylated, depending on the reaction conditions. The thermal and morphological properties of the resulting polymers were also discussed.
Fluorene-containing, spiro-type, conjugated polymers were synthesized via the cyclopolymerization of dipropargylfluorenes (2-substituted, X=H, Br, Ac, NO 2 ) with various transition metal catalysts. The polymerization of dipropargylfluorenes proceeded well using Mo-based catalysts to give a high polymer yield. The catalytic activities of the Mo-based catalysts were found to be more effective than those of W-based catalysts. The palladium (II) chloride also increased the polymer yield of the polymerization. The polymer structure of poly(dipropargylfluorene)s was characterized by such instrumental methods as NMR ( 1 H-, 13 C-), IR, UV-visible spectroscopies, and elemental analysis as having the conjugated polymer backbone bearing fluorene moieties. The 13 C-NMR spectral data on the quaternary carbon atoms in polymers indicated that the conjugated cyclopolymers have the six-membered rings majorly. The poly(dipropargylfluorene) derivatives were completely soluble in halogenated and aromatic hydrocarbons such as methylene chloride, chloroform, benzene, toluene, and chlorobenzene. The poly(dipropargylfluorene) derivatives were thermally more stable than poly(dipropargylfluorene) itself, and X-ray diffraction analyses revealed that the polymers are mostly amorphous. The photoluminescence peaks of the polymers were observed at about 457-491 nm, depending on the substituents of fluorene moieties.
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