Dilithium manganese oxide (LMO) thin film was newly fabricated as an active material on a fluorinated-tin-oxide pre-coated glass electrode by a wet process. A stable LMO precursor solution was developed through the reaction of lithium and manganese acetates with butylamine in ethanol. A spin-coated precursor film was heat-treated at 500 °C in air for 0.5 h. The X-ray diffraction pattern indicates that the resultant film consists of layer-structured LMO crystals. The X-ray photoelectron spectra of LMO thin film suggests that the ratio of Mn3+/Mn4+ is 1/4, and the chemical formula can be expressed as Li2MnO2.9. A device was assembled with O-deficient LMO and TiO2 thin films as each active material, along with an electrolytic solution involving LiPF6. The charging voltages (2.67 and 1.45 V) of this device were recorded by applying a constant current of 0.2 mA and using 1-sun irradiation with no external power supply, respectively. The voltages delivered by this cobalt-free device were 0.63 and 0.13 V higher, respectively, than the corresponding device assembled with lithium cobalt oxide as a cathodic active material.
A single-walled carbon nanotube/anatase (SWCNT/anatase) composite thin film with a transmittance of over 70% in the visible-light region was fabricated on a quartz glass substrate by heat treating a precursor film at 500 °C in air. The precursor film was formed by spin coating a mixed solution of the titania molecular precursor and well-dispersed SWCNTs (0.075 mass%) in ethanol. The anatase crystals and Ti3+ ions in the composite thin films were determined by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. The effect of the heating process on the SWCNTs was analyzed using Raman spectroscopy. The composite film showed an even surface with a scratch resistance of 4H pencil hardness, as observed using field-emission scanning electron microscopy and atomic force microscopy. The electrical resistivity and optical bandgap energy of the composite thin film with a thickness of 100 nm were 6.6 × 10−2 Ω cm and 3.4 eV, respectively, when the SWCNT content in the composite thin film was 2.9 mass%. An anodic photocurrent density of 4.2 μA cm−2 was observed under ultraviolet light irradiation (16 mW cm−2 at 365 nm) onto the composite thin film, thus showing excellent properties as a photoelectrode without conductive substrates.
Titania precursor films were electrosprayed on a quartz glass substrate, which was pre-modified with an ultra-thin film obtained by spin-coating a single-walled carbon nanotube (SWCNT) dispersed solution. The X-ray diffraction patterns of the thin films obtained by heat-treating the precursor films at 500 °C in air for 1 h indicated that the formed crystals were anatase. A new route to fabricate transparent thin films on the insulating substrate via electrospray deposition (ESD) was thus attained. The photoluminescence spectrum of the thin film showed a peak at 2.23 eV, assignable to the self-trapped exciton of anatase. The Raman spectrum of the thin film demonstrated that heat treatment is useful for removing SWCNTs. The thin film showed a water contact angle of 14 ± 2° even after being kept under dark conditions for 1 h, indicating a high level of hydrophilicity. Additionally, the thin film had a super-hydrophilic surface with a water contact angle of 1 ± 1° after ultraviolet light irradiation with an intensity of 4.5 mW cm–2 at 365 nm for 1 h. The importance of Ti3+ ions in the co-present amorphous phase, which was dominantly formed via the ESD process, for hydrophilicity was also clarified by means of X-ray photoelectron spectroscopy.
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