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Al2O3 layers were deposited onto electrodes by atomic layer deposition. Solubility and electron-transport blocking were tested. Films deposited onto fluorine-doped tin oxide (FTO, F:SnO2/glass) substrates blocked electron transfer to redox couples (ferricyanide/ferrocyanide) in aqueous media. However, these films were rapidly dissolved in 1 M NaOH (≈100 nm/h). The dissolution was slower in 1 M H2SO4 (1 nm/h) but after 24 h the blocking behaviour was entirely lost. The optimal stability was reached at pH 7.2 where no changes were found up to 24 h and even after 168 h of exposure the changes in the blocking behaviour were still minimal. This behaviour was also observed for protection against direct reduction of FTO.

For proper function of the negative electrode of dye-sensitized and perovskite solar cells, the deposition of a nonporous blocking film is required on the surface of F-doped SnO2 (FTO) glass substrates. Such a blocking film can minimise undesirable parasitic processes, for example, the back reaction of photoinjected electrons with the oxidized form of the redox mediator or with the hole-transporting medium can be avoided. In the present work, thin, transparent, blocking TiO2 films are prepared by semi-automatic spray pyrolysis of precursors consisting of titanium diisopropoxide bis(acetylacetonate) as the main component. The variation in the layer thickness of the sprayed films is achieved by varying the number of spray cycles. The parameters investigated in this work were deposition temperature (150, 300 and 450 °C), number of spray cycles (20–200), precursor composition (with/without deliberately added acetylacetone), concentration (0.05 and 0.2 M) and subsequent post-calcination at 500 °C. The photo-electrochemical properties were evaluated in aqueous electrolyte solution under UV irradiation. The blocking properties were tested by cyclic voltammetry with a model redox probe with a simple one-electron-transfer reaction. Semi-automatic spraying resulted in the formation of transparent, homogeneous, TiO2 films, and the technique allows for easy upscaling to large electrode areas. The deposition temperature of 450 °C was necessary for the fabrication of highly photoactive TiO2 films. The blocking properties of the as-deposited TiO2 films (at 450 °C) were impaired by post-calcination at 500 °C, but this problem could be addressed by increasing the number of spray cycles. The modification of the precursor by adding acetylacetone resulted in the fabrication of TiO2 films exhibiting perfect blocking properties that were not influenced by post-calcination. These results will surely find use in the fabrication of large-scale dye-sensitized and perovskite solar cells.

Systematic in situ Raman microdroplet spectroelectrochemical (Raman-μSEC) characterization of copper (I) thiocyanate (CuSCN) prepared using electrodeposition from aqueous solution on various substrates (carbon-based, F-doped SnO2) is presented. CuSCN is a promising solid p-type inorganic semiconductor used in perovskite solar cells as a hole-transporting material. SEM characterization reveals that the CuSCN layers are homogenous with a thickness of ca. 550 nm. Raman spectra of dry CuSCN layers show that the SCN− ion is predominantly bonded in the thiocyanate resonant form to copper through its S−end (Cu−S−C≡N). The double-layer capacitance of the CuSCN layers ranges from 0.3 mF/cm2 on the boron-doped diamond to 0.8 mF/cm2 on a glass-like carbon. In situ Raman-μSEC shows that, independently of the substrate type, all Raman vibrations from CuSCN and the substrate completely vanish in the potential range from 0 to −0.3 V vs. Ag/AgCl, caused by the formation of a passivation layer. At positive potentials (+0.5 V vs. Ag/AgCl), the bands corresponding to the CuSCN vibrations change their intensities compared to those in the as-prepared, dry layers. The changes concern mainly the Cu−SCN form, showing the dependence of the related vibrations on the substrate type and thus on the local environment modifying the delocalization on the Cu−S bond.

This paper evaluates the influence of the morphology, surface area, and surface modification of carbonaceous additives on the performance of the corresponding cathode in a lithium–sulfur battery. The structure of sulfur composite cathodes with mesoporous carbon, activated carbon, and electrochemical carbon is studied by X-ray diffraction, nitrogen adsorption measurements, and Raman spectroscopy. The sulfur cathode containing electrochemical carbon with the specific surface area of 1606.6 m2 g−1 exhibits the best electrochemical performance and provides a charge capacity of almost 650 mAh g−1 in cyclic voltammetry at a 0.1 mV s−1 scan rate and up to 1300 mAh g−1 in galvanostatic chronopotentiometry at a 0.1 C rate. This excellent electrochemical behavior is ascribed to the high dispersity of electrochemical carbon, enabling a perfect encapsulation of sulfur. The surface modification of carbonaceous additives by TiO2 has a positive effect on the electrochemical performance of sulfur composites with mesoporous and activated carbons, but it causes a loss of dispersity and a consequent decrease of the charge capacity of the sulfur composite with electrochemical carbon. The composite of sulfur with TiO2-modified activated carbon exhibited the charge capacity of 393 mAh g−1 in cyclic voltammetry and up to 493 mAh g−1 in galvanostatic chronopotentiometry. The presence of an additional Sigracell carbon felt interlayer further improves the electrochemical performance of cells with activated carbon, electrochemical carbon, and nanocrystalline TiO2-modified activated carbon. This positive effect is most pronounced in the case of activated carbon modified by nanocrystalline TiO2. However, it is not boosted by additional coverage by TiO2 or SnO2, which is probably due to the blocking of pores.

Planar perovskite solar cells were fabricated on F-doped SnO2 (FTO) coated glass substrates, with 4,4’-((1E,1’E)-((1,2,4-thiadiazole-3,5-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(N,N-di-p-tolylaniline) (bTAThDaz) as hole transport material. This imine was synthesized in one step reaction, starting from commercially available and relatively inexpensive reagents. Electrochemical, optical, electrical, thermal and structural studies including thermal images and current-voltage measurements of the full solar cell devices characterize the imine in details. HOMO-LUMO of bTAThDaz were investigated by cyclic voltammetry (CV) and energy-resolved electrochemical impedance spectroscopy (ER-EIS) and were found at −5.19 eV and −2.52 eV (CV) and at −5.5 eV and −2.3 eV (ER-EIS). The imine exhibited 5% weight loss at 156 °C. The electrical behavior and photovoltaic performance of the perovskite solar cell was examined for FTO/TiO2/perovskite/bTAThDaz/Ag device architecture. Constructed devices exhibited good time and air stability together with quite small effect of hysteresis. The observed solar conversion efficiency was 14.4%.

Titania nanofibers were fabricated using the industrial NanospiderTM technology. The preparative protocol was optimized by screening various precursor materials to get pure anatase nanofibers. Composite films were prepared by mixing a commercial paste of nanocrystalline anatase particles with the electrospun nanofibers, which were shortened by milling. The composite films were sensitized by Ru-bipyridine dye (coded C106) and the solar conversion efficiency was tested in a dye-sensitized solar cell filled with iodide-based electrolyte solution (coded Z960). The solar conversion efficiency of a solar cell with the optimized composite electrode (? = 7.53% at AM 1.5 irradiation) outperforms that of a solar cell with pure nanoparticle film (? = 5.44%). Still larger improvement was found for lower light intensities. At 10% sun illumination, the best composite electrode showed ? = 7.04%, referenced to that of pure nanoparticle film (? = 4.69%). There are non-monotonic relations between the film's surface area, dye sorption capacity and solar performance of nanofiber-containing composite films, but the beneficial effect of the nanofiber morphology for enhancement of the solar efficiency has been demonstrated.

Nanocrystalline TiO2 films were explored for the first time as electrode material for a rechargeable lithium intercalation cell, i.e., Li/LiCF3SO3 + PC/TiO2. Two kinds of nanocrystalline films, TiO2 F387 (Degussa) and TiO2 colloid-240, were investigated. These films exhibited excellent performance renderings them a promising choice for secondary battery applications. At a current density of 0.01 mA/cm2, two voltage plateaus at 1.78 and 1.89 V were observed for TiO2 F387 films during charge and discharge, respectively. The TiO2 electrode charge capacity per unit weight rose with decreasing current density. The highest capacity, obtained at a current density of 0.005 mA/cm2 and a final discharge voltage of 1.4 V, was 265 mAh/g corresponding to a lithium insertion ratio of x = 0.8. Nanocrystalline TiO2 colloid-240 films showed a similar performance. The cycle life of a TiO2 colloid-240 cell at a high current density was found to be excellent; a capacity loss lower than 14% has been observed over 100 charge/discharge cycles.