Pre-existence of HxWO3 in e-beam deposited WO3 films

Structural and optical properties of e-beam deposited tungsten trioxide (WO₃) films in as-deposited and electrochemically coloured states were investigated by spectrophotometric and XRD techniques. These investigations have shown the as-deposited WO₃ films to be porous and with small amount of H_xWO₃ pre-existing in them. The films further facilitate insertion of H⁺ ions on colouration resulting in tetragonal H_xWO₃ with a = 4.74Å and c = 3.19Å.     

Electrochemical performance of In2O3 thin film electrode in lithium cell

Indium oxide (In₂O₃) coating on Pt, as an electrode of thin film lithium battery was carried out by using cathodic electrochemical synthesis in In₂(SO₄)₃ aqueous solution and subsequently annealing at 400 °C. The coated specimens were characterized by X-ray photoelectron spectroscopy (XPS) for chemical bonding, X-ray diffraction (XRD) for crystal structure, scanning electron microscopy (SEM) for surface morphology, cyclic voltammetry (CV) for electrochemical properties, and charging/discharging test for capacity variations. The In₂O₃ coating film composed of nano-sized particles about 40 nm revealing porous structure was used as the anode of a lithium battery. During discharging, six lithium ions were firstly reacted with In₂O₃ to form Li₂O and In, and finally the Li_4.33In phase was formed between 0.7 and 0.2 V, revealing the finer particles size about 15 nm. The reverse reaction was a removal of Li⁺ from Li_4.33In phase at different oxidative potentials, and the rates of which were controlled by the thermodynamics state initially and diffusion rate finally. Therefore, the total capacity was increased with decreasing current density. However, the cell delivering a stable and reversible capacity of 195 mAh g⁻¹ between 1.2 and 0.2 V at 50 μA cm⁻² may provide a choice of negative electrode applied in thin film lithium batteries.     

Study of the Li insertion into V2O5 films deposited by CVD onto various substrates

Vanadium oxide films were synthesised by chemical vapour deposition (CVD) from pure of triisopropoxyvanadium oxide (VO(OC₃H₇)₃) and oxygen as precursors. The influence of the substrate on the crystallinity of the vanadium oxide films was studied before and after annealing at 500 °C. On mica substrates, as-deposited film was composed of crystalline V₂O₅ as revealed by XRD. On Pt, Ti, stainless steel, glass and F-doped SnO₂ substrates, an annealing procedure was required to get V₂O₅. SEM investigations have clearly evidence V₂O₅ plates but the kinetics growth seems to be strongly dependent on the nature of the substrate. The insertion/extraction of Li⁺ into the host structure was investigated in 1 M LiClO₄-PC with annealed V₂O₅ films deposited on Ti, Pt and stainless steel substrates. The best electrochemical performances were obtained in the potential range 3.8–2.8 V versus Li/Li⁺ with V₂O₅ films deposited onto stainless steel substrate: the reversible capacity reaches after subsequent cycles was about 115 mAh g⁻¹ (rate C/23). In a wider potential range (between 3.8 and 2.2 V versus Li/Li⁺), V₂O₅ deposited onto Ti substrate exhibited the higher electrochemical performances (220 mAh g⁻¹ for a rate of C/23).     

Electrochemical intercalation of lithium ions into LiV3O8 in an aqueous electrolyte

Electrochemical intercalation of lithium ions from a saturated LiNO₃ aqueous electrolyte solution into LiV₃O₈ prepared by a solid-state reaction at 680 °C was studied with cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Results show that there are three steps of intercalation in the presence of an aqueous electrolyte, in agreement with those previously observed with organic liquid electrolytes. In addition, variations of several parameters including the charge transfer resistance (R_ct), the capacitance of the double layer (C_DL), the Warburg diffusion impedance (Z_w), and diffusion coefficient of lithium ions (DLi₊$D_{\text{L}{\text{i}}^{+}}$) during the intercalation process are reported.     

Optical properties of sol–gel deposited Al2O3 films

Highly transparent, uniform and corrosion resistant Al₂O₃ films were prepared on stainless-steel and quartz substrates by the sol–gel process from stable coating solutions using aluminum-sec-butoxide, Al(OBu^s)₃ as precursor, acetylacetone, AcAcH as chelating agent and nitric acid, HNO₃, as catalyzer. Films up to 1000 nm thick were prepared by multiple spin coating deposition, and were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), optical spectroscopy and micro Vickers hardness test. XRD of the film heat treated at 400°C showed that they had an amorphous structure. XPS confirmed that they were stoichiometric Al₂O₃. The refractive index (n) and extinction coefficient (k) were found to be n=1.56±0.01 and k=0.003±0.0002 at 600 nm, respectively. The surface microhardness and corrosion resistance investigations showed that Al₂O₃ films improved the surface properties of stainless-steel substrates.     

Electrochemical performance of all-solid-state lithium secondary batteries improved by the coating of Li2O-TiO2 films on LiCoO2 electrode

All-solid-state lithium secondary batteries using LiCoO₂ particles coated with amorphous Li₂O-TiO₂ films as an active material and Li₂S-P₂S₅ glass-ceramics as a solid electrolyte were fabricated; the electrochemical performance of the batteries was investigated. The interfacial resistance between LiCoO₂ and solid electrolyte was decreased by the coating of Li₂O-TiO₂ films on LiCoO₂ particles. The rate capability of the batteries using the LiCoO₂ coated with Li₂Ti₂O₅ (Li₂O·2TiO₂) film was improved because of the decrease of the interfacial resistance of the batteries. The cycle performance of the all-solid-state batteries under a high cutoff voltage of 4.6 V vs. Li was highly improved by using LiCoO₂ coated with Li₂Ti₂O₅ film. The oxide coatings are effective in suppressing the resistance increase between LiCoO₂ and the solid electrolyte during cycling. The battery with the LiCoO₂ coated with Li₂Ti₂O₅ film showed a large initial discharge capacity of 130 mAh/g and good capacity retention without resistance increase after 50 cycles at the current density of 0.13 mA/cm².     

Structure–property relationships in electrochromic WO3 films deposited by reactive sputtering

WO_x electrochromic (EC) films deposited by DC magnetron sputtering technique were investigated by XRD and STM measurements. The reversible microstructure changes of the WO_x film between the bleached and colored EC states were revealed. The study indicates that the amorphous as-deposited WO_x film (a-WO_x) is of amorphous microstructure both in bleached and colored states; however, the crystalline WO_x (c-WO_x) is stoichiometric triclinic lattice WO₃ in bleached state (the lattice parameters: a=7.2944 Å, b=7.4855 Å, c=3.7958 Å, α=89.38°, β=90.42°, γ=90.80°), and changes into nonstoichiometric tetragonal lattice WO_2.9 in colored state (a=b=5.336 Å, c=3.788 Å, α=β=γ=90°). The surface morphologies of the colored WO_x films are very different from those of the bleached WO_x films.     

CuInSe2 thin films deposited by UV laser ablation

Application of pulsed laser ablation method for deposition of CuInSe₂ films was studied. The special time–temperature regime was developed. The homogeneous amorphous and polycrystalline CuInSe₂ films were prepared and investigated with XRD, SEM-EDS and optical spectroscopy.     

Structural and electrochemical studies of WO3 films deposited by pulsed spray pyrolysis

Transparent conductive and WO₃ electrochromic thin films were deposited by spray pyrolysis technique. The films were deposited using solutions of WCl₆ in dimethylformamide on SnO₂:F (FTO) substrates with different sheet resistances. Noticeable effects of substrate on structural, morphological and optical properties of the WO₃ films and on its electrochromic behavior are presented and discussed. Hexagonal and monoclinic WO₃ structures were obtained on amorphous glass substrates; also the monoclinic structure on polycrystalline FTO substrates was obtained. Cyclic structural changes during the colored and blanched states were found from XRD and electron diffraction result analysis: The hydrogen tungsten bronze in the tetragonal phase after the hydrogen extraction change to the original WO₃ monoclinic phase.     

The dependence of the chemical potential of WO3 films on hydrogen insertion

Knowledge of the chemical potential of electrochromic films coloured by hydrogen is important for matching the elements of an electrochromic device, for understanding the colouring mechanism and for obtaining information about the microscopic structure of the film. The dependence of the chemical potential on the hydrogen concentration was measured electrochemically for tungsten oxide films of different crystallinity and water content. A new method for determining the chemical potential by catalytic coloration by hydrogen gas is introduced. It revealed that the increase in electromotive force with increasing crystallinity is due only to different binding energies of the protons. We expect the protons to be located in the centres of hexagons, which are created by WO₆ octahedra. According to our model, amorphous sputtered films show a hexagonal structure which is similar to that of evaporated films, but the hexagons are connected, leading to more hexagon centre sites, which increases the electromotive force.     

Electrochemical instability of LiV3O8 as an electrode material for aqueous rechargeable lithium batteries

We demonstrate the unsuitability of LiV₃O₈ as an electrode material for aqueous rechargeable lithium batteries on simple but solid grounds: the compound is unstable under typical battery operation conditions, where it slowly dissolves as reflected in the yellow color acquired by the electrolyte. This can be the origin of the poor performance of the aqueous batteries based on this compound.     

Optical and structural properties of pulsed laser deposited Ti:Al2O3 thin films

Spectrally selective solar absorber coatings using metal–dielectric composites offer a high degree of flexibility since their solar selectivity can be optimized by the proper choices of constituents, coating thickness, metal particle concentration, size, shape, and orientation. In this article, Ti:Al₂O₃ composite films of various Ti contents were prepared by the pulsed laser deposition technique, and their structural and optical properties were investigated by scanning electron microscope, X-ray photoelectron spectroscope, and X-ray diffraction methods. The results demonstrate promising solar spectrally selective behavior indicating Ti:Al₂O₃ composite as an excellent choice for solar thermal applications.     

Photoelectrochemical properties of spray deposited n-ZnIn2Se4 thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been prepared by spraying a mixture of an equimolar aqueous solution of zinc sulphate (ZnSO₄), indium trichloride (InCl₃), and selenourea (CH₄N₂Se), onto preheated fluorine-doped tin oxide (FTO)-coated glass substrates at optimized conditions of substrate temperature and a solution concentration. The photoelectrochemical (PEC) cell configuration of n-ZnIn₂Se₄/1 M (NaOH+Na₂S+S)/C has been used for studying the current voltage (I–V), spectral response, and capacitance voltage (C–V) characteristics of the films. The PEC study shows that the ZnIn₂Se₄ thin films exhibited n-type conductivity. The junction quality factor in dark (n_d) and light (n_l), series and shunt resistance (R_s and R_sh), fill factor (FF) and efficiency (η) for the cell have been estimated. The measured (FF) and η of the cell are, respectively, found to be 0.435% and 1.47%.     

MgH2 thin films deposited by one-step reactive plasma sputtering

The morphology, crystal structure, hydrogen content, and sorption properties of magnesium hydride thin films prepared by reactive plasma-assisted sputter deposition were investigated. Few micrometers-thick films were deposited on Si and SiO₂/Si substrates, at low pressure (0.4 Pa) and close to room temperature using (Ar + H₂) plasma with H₂ fraction in the range 15–70%. The microstructure and hydrogen content of the films are closely related to the surface temperature and hydrogen partial pressure during the deposition process. Operating in pulsed-plasma mode allows the hydrogenation rate of the MgH₂ thin film to top up to 98%, thereby producing a nearly fully hydrogenated film in a single-step process. The positive effect of the pulsed process is explained by the significant decrease in the whole energy flux incident on the surface and the favourable impact of the transient process for the rearrangement/relaxation of the materials. As for the hydrogen storage properties, desorption experiments and cycling of the films show the destabilizing effect of Mg₂Si formation at the interface between the film and the Si substrate resulting in a drastically increased desorption kinetics compared to less reactive SiO₂ substrate. However, the reaction is regrettably not reversible upon hydrogenation and the hydrogen storage capacity is consequently reduced upon cycling. Nevertheless, the deposition process carried out on inert substrates would offer true potential for reversible storage. Finally, our experimental results, which show the possibility to preferentially grow the metastable medium pressure γ-MgH₂ phase, open possibilities for the synthesis of more complex metastable phases such as magnesium-based ternary compounds.     

Electrical conductivity of a new solid electrolyte glass material Li2OLiNbO3B2O3

With a view to the development of a lithium—borate based glass material with high ionic conductivity at the lowest possible temperature, the conductivities of different compositions of the Li₂OB₂O₃ glass system have been studied. The effect of LiNbO₃ addition on the temperature dependent conductivity of the Li₂OB₂O₃ (40:60 mol%) system, which shows maximum conductivity within the homogeneous glass formation region, was observed. The enhancement in the conductivity, 1.43 × 10^?2 (ohm cm)^?1 at 623 K, has been attributed to the increase in Li ion concentration and to its mobility which is due to vacant sites provided by the pentavalent Nb ion of Nb₂O₅. The conductivities achieved in the present investigation have been compared with earlier reports on similar systems. This material may be suitable as an electrolyte for application to power sources.     

Chemical composition dependence of morphological and optical properties of Cu2ZnSnS4 thin films deposited by sol-gel sulfurization and Cu2ZnSnS4 thin film solar cell efficiency

The properties of Cu₂ZnSnS₄ (CZTS) thin films deposited by sol-gel sulfurization were investigated as a function of the chemical composition of the sol-gel solutions used. The chemical composition ratio Cu/(Zn+Sn) of the sol-gel solution was varied from 0.73 to 1.00, while the ratio Zn/Sn was kept constant at 1.15. CZTS films deposited using sol-gel solutions with Cu/(Zn+Sn)<0.80 exhibited large grains. In addition, the band gaps of these Cu-poor CZTS thin films were blue shifted. Solar cells with the structure Al/ZnO:Al/CdS/CZTS/Mo/soda lime glass were fabricated under non-vacuum conditions. The solar cell with the CZTS layer deposited using the sol-gel solution with Cu/(Zn+Sn)=0.80 exhibited the highest conversion efficiency of 2.03%.     

Electro deposited In2S3 buffer layers for CuInS2 solar cells

We report the electro deposition of In₂S₃ buffer layers for CuInS₂ solar cells. All materials and deposition conditions were selected taking into account environmental, economic and technological aspects of a potential transfer to large volume industrial production. Different bath compositions and electro deposition parameters were studied. The obtained films exhibited complete substrate coverage, confirmed by SEM and XPS. In/S ratio close to 2/3 was obtained. XPS measurements detected the presence of indium hydroxide, transforming into oxide upon anneal at 200 °C. Maximum photoelectric conversion efficiency of 7.1% was obtained, limited mainly by a low fill factor (51%). Further process optimization is expected to lead to efficiencies comparable to CdS buffers. So far, open-circuit voltages as high as 660 mV were demonstrated.     

Electrochemical properties of negative SiMox electrodes deposited on a roughened substrate for rechargeable lithium batteries

To replace conventional carbon, silicon has been widely proposed as a next-generation negative electrode (anode) material for lithium-ion batteries. In this study, Si and SiMo_x-alloy deposited by an RF-magnetron sputtering system is investigated by means of X-ray diffraction, ex situ Raman spectroscopy and transmission electron microscopy. Electrochemical tests are conducted and four different Si and SiMo_x-alloy electrodes and their structures and textual properties are characterized with X-ray photoelectron spectroscopy. The surface morphologies of the electrodes are also observed using field-emission scanning electron microscopy. The electrochemical properties of the electrodes are examined through cycling tests and electrochemical impedance spectroscopy. The results show that rough Cu foil and Mo as alloy materials help Si to retain its discharge capacity and overcome volume expansion during charging and discharging. After a few cycles, the Si electrode severely loses capacity, whereas the SiMo_x-alloy electrodes display good cycle retention and high capacity. The SiMo_0.79 electrode gives an initial capacity of 1319 mAh g⁻¹ that decreases to 1180 mAh g⁻¹ after 100 cycles (89.4%).     

Electrochemical lithium storage of TiO2 hollow microspheres assembled by nanotubes

TiO₂ hollow microspheres with the shell consisting of nanotubes have been successfully synthesized via a template-free hydrothermal process and subsequent treatments. The electrochemical properties of the anatase sample have been investigated by cyclic voltammetry and galvanostatic method. The initial Li insertion/extraction capacity at a current density of 0.2 C reach 290 and 232 mAh g⁻¹ respectively. Moreover, as-prepared TiO₂ delivers a reversible capacity of ca. 150 mAh g⁻¹ after 500 cycles at 1 C, and it also shows superior high rate performance (e.g., 90 mAh g⁻¹ at 8 C) without any modification.     

Electrochemical and structural studies of LiCo1/3Mn1/3Fe1/3PO4 as a cathode material for lithium ion batteries

A solid-state reaction to synthesize a lithium multi-transition metal phosphate LiCo_1/3Mn_1/3Fe_1/3PO₄ is used in this work, which has a high voltage of 3.72 V and capacity of 140 mAh g⁻¹ at a 0.05 C rate. From the in-situ XRD analysis, LiCo_1/3Mn_1/3Fe_1/3PO₄ has shown a high stability during cell charge/discharge, even operating at 5 V, which is due to the stable olivine structure. Although all the transition metals Co²⁺, Mn²⁺ and Fe²⁺ are at the same 4c site of the LiCo_1/3Mn_1/3Fe_1/3PO₄ structure, they seem to have different chemical activities and reflect on the electrochemical performance. The capacity contributed by the Co²⁺/Co³⁺ redox couple is only 20 mAh g⁻¹, which is less than that of the Fe²⁺/Fe³⁺ and Mn²⁺/Mn³⁺ redox couples. This is because of the fact that the diffusivity of lithium ion for the Co²⁺/Co³⁺ redox couple is 10⁻¹⁶ cm² s⁻¹ which is one order less than that of the Fe²⁺/Fe³⁺ and Mn²⁺/Mn³⁺ redox couples in LiCo_1/3Mn_1/3Fe_1/3PO₄.