Synthesis of spherical LiMn2O4 microparticles by a combination of spray pyrolysis and drying method

Lithium manganese oxide (LiMn₂O₄) has been synthesized by a spray pyrolysis method from the precursor solution; LiNO₃ and Mn(NO₃)₂·6H₂O were stoichiometrically dissolved into distilled water. The synthesized LiMn₂O₄ particles exhibited a pure cubic spinel structure in the X-ray diffraction (XRD) patterns, however they were spherical hollow spheres for various concentrations of precursor solution. Thus, the as-prepared LiMn₂O₄ particles were then ground in a mortar and dispersed into distilled water. To make a well dispersed slurry solution, a dispersion agent was also added into the slurry solution. The LiMn₂O₄ microparticles with a spherical nanostructure were finally prepared by a spray drying method from the slurry solution. The tap density of the LiMn₂O₄ microparticle prepared by a combination of spray pyrolysis and drying method was larger than that by a conventional spray pyrolysis method.The as-prepared samples were sintered at 750 °C for 1 h in air and used as cathode active materials for lithium batteries. Test experiments in the electrochemical cell Li|1 M LiClO₄ in EC:DEC = 1:1|LiMn₂O₄ demonstrate that the sample prepared by the present method is a promising cathode active material for 4 V lithium-ion batteries at high-charge-discharge and elevated temperature operation. The LiMn₂O₄ compounds by the combination of spray pyrolysis and drying method are superior to that by the conventional spray pyrolysis method in terms of electrochemical characteristics and tap density.     

Three-dimensional porous amorphous SnO2 thin films as anodes for Li-ion batteries

Three-dimensional (3D) porous amorphous SnO₂ thin films were deposited on Ni foam substrates by Electrostatic Spray Deposition (ESD) technique as anodes for Li-ion batteries. These films display good capacity retention of 94.8% after 100 cycles at 0.5 C and rate capability of 362 mAh/g at 10 C. The improved performance originates from the fact that the 3D porous structure offers a “buffer zone” to accommodate the large volume change during cycling, and the foam-like substrate maximizes the contact area between electrode and electrolyte. The facile ESD method can be potentially extended to prepare other 3D porous functional materials.     

Electrochemical properties of amorphous GeOx-C composite microspheres prepared by a one-pot spray pyrolysis process

Amorphous GeO₂-GeO-C (GeO_x-C) composite powders, containing a small amount of the GeC phase, are prepared by a one-pot spray pyrolysis process. The GeO_x-C composite powders have a completely spherical shape and are non-aggregated. The Ge 3d components in the XPS spectrum of the composite occupy 53.3%, 40.1%, and 6.6% of the total for GeO₂, GeO, and GeC, respectively. The amount of amorphous carbon in the GeO_x-C composite powder is estimated at 18.3%, based on the TG and XPS analysis. The initial discharge and charge capacities of the GeO_x-C composite powders at a current density of 1 A g⁻¹ are 1873 and 908 mA h g⁻¹, respectively. The discharge capacities of the GeO_x-C composite and commercial GeO₂ powders for the 1200th cycle are 723 and 169 mA h g⁻¹, respectively, and their corresponding capacity retentions from the 2nd cycle are 70.1% and 19.0%, respectively. The high structural stability of the composite during repeated lithium insertion and desertion processes results in excellent long-term cycling performance.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Synthesis of Zn2SnO4 anode material by using supercritical water in a batch reactor

Zn₂SnO₄ anode powders were successfully synthesized using supercritical water (SCW) and metal salt solutions with 10 min reaction time. Effect of NaOH concentration, Zn to Sn ratio, and synthesis temperature were studied with a SCW batch reactor. X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge/discharge cycling tests were employed to characterize the physical properties and electrochemical performance of the as-prepared samples. Alkaline solution concentration and synthesis temperature played a key role in the production of single-phase Zn₂SnO₄ powders. At a solution concentration of 0.3 M NaOH and a molar ratio of Zn:Sn = 2:1 at 400 °C and 30 MPa, the average size range of the pure Zn₂SnO₄ powders was 0.5-1.0 μm, and the morphology was nearly uniform and cubic-like in shape. The initial specific discharge capacity of the Zn₂SnO₄ powders prepared at this condition was 1526 mAh/g at a current density of 0.75 mA/cm² in 0.05-3.0 V, and their irreversible capacity loss was 433 mAh/g. The discharge capacities of the Zn₂SnO₄ powders decreased with cycling and remained at 856 mAh/g after 50 cycles, which was 56% of the initial capacity.     

Electrochemical properties of SnO2/carbon composite materials as anode material for lithium-ion batteries

SnO₂/carbon composite anode materials were synthesized from SnCl₄·5H₂O and sucrose via a hydrothermal route and a post heat-treatment. The synthesized spherical SnO₂/carbon powders show a cauliflower-like micro-sized structure. High annealing temperature results in partial reduction of SnO₂. Metallic Sn starts to emerge at 500 °C. High Sn content in SnO₂/carbon composite is favorable for the increase of initial coulombic efficiency but not for the cycling stability. The SnO₂/carbon annealed at 500 °C exhibits high specific capacity (∼400 mAh g⁻¹), stable cycling performance and good rate capability. The generation of Li₂O in the first lithiation process can prevent the aggregation of active Sn, while the carbon component can buffer the big volume change caused by lithiation/delithiation of active Sn. Both of them make contribution to the better cycle stability.     

Effect of precursor characteristics on zirconia and ceria particle morphology in spray pyrolysis

Ultrasonic spray pyrolysis of acetate-based precursors with precisely measured precursor drop size was employed to produce ZrO₂ and CeO₂ particles. A bimodal size distribution of the product particles indicates a significant influence of the gas-to-particle conversion mechanism in addition to the conventionally accepted one-particle-per-drop mechanism. Due to the differences in solubility of the precursors, ZrO₂ particles are spherical in shape and smooth on their surfaces while the CeO₂ particles are bowl-like in shape with uneven surfaces. Spherical and monodispersed particles with a peak diameter <100 nm can be obtained by reducing the precursor concentrations to 0.01 wt.% in both the different precursor system.     

A facile route to carbon-coated SnO2 nanoparticles combined with a new binder for enhanced cyclability of Li-ion rechargeable batteries

Carbon-coated SnO₂ nanoparticles were prepared by a novel facile route using commercial SnO₂ nanoparticles treated with concentrated sulfuric acid in the presence of sucrose at room temperature and ambient pressure. The key features of this method are the simple procedure, low energy consumption, and inexpensive and non-toxic source materials. As-prepared core/shell nanoparticles were characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The electrochemical measurements showed that the carbon-coated SnO₂ nanoparticles with 10% carbon and using carboxymethyl cellulose (CMC) as a binder displayed the best electrochemical performance with the highest specific capacity of 502 mAh g⁻¹ after 50 cycles at a current density of 100 mA g⁻¹. In addition, owing to the water solvability of CMC, the usage of CMC as binder makes the whole electrode fabrication process cheaper and more environmental friendly.     

Electrochemistry of a new carbon-rich fluorine-doped tin oxide (CFTO) material as a powder electrode in chloride electrolytes

The electrochemical behavior of a conductive carbon-rich fluorine-doped tin oxide (CFTO) powder synthesized via the sol-gel process was investigated by studying the chloride oxidation reaction in aqueous media with the help of a cavity microelectrode (CME) without any binding additive. This new electroactive compound was found to be very efficient with respect to the chloride-chlorine reaction which was reversible in the 2-7 pH range. The CFTO powder electrode was characterized by linear sweep voltamperometry and electrochemical impedance measurements. On the basis of numerical simulations, impedance spectra were interpreted by considering a porous electrode behavior with a coupled concentration and potential axial gradients. The experimental data were quantitatively accounted for by considering the parallel combination of a number of cylindrical pores. On the CFTO powder, the chloride oxidation mechanism was simply described by a single electron exchange, in accordance with a Volmer-Tafel mechanism.     

Evidence by EIS of the interaction between proteins and tin oxide electrode surface

Macromolecules like proteins are able to adhere to tin oxide electrodes at open circuit potential as proved by electrogravimetry experiments. In this work, electrochemical impedance studies were performed at aqueous electrolyte/F- or Sb-doped semiconducting tin oxide interfaces, including natural seawater. By this way, it was possible to characterize the potential dependence of the interfacial capacitance in various physicochemical conditions, without or in the presence of bovine serum albumin (BSA). In the potential range where tin oxide is in the depletion regime (blocking interface), a capacitance excess is evidenced which can be attributed to the formation of surface states which are the signature of chemical bonding. By simulating the so-called surface state capacitance, three states have been pointed out. They are centred at 0.7, 0.9 and 1.1 eV in the tin oxide bandgap. On the basis of experimental arguments, the state at 1.1 eV was ascribed to the OH-terminated tin oxide surface, the two other states were found to be specific of the interaction of organic matter with the oxide surface. In the presence of BSA, the density of surface atoms (about 10¹³ cm⁻²) involved in bonding is of the order of magnitude of the surface concentration of one BSA monolayer. The lasting character of these bonds was also shown. This finding shows the definitive protein immobilisation at the SnO₂ surface.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Co2SnO4–multiwalled carbon nanotubes composite as a highly reversible anode material for lithium-ion batteries

We report a facile strategy to synthesize the composite of Co₂SnO₄ nanoparticles and multiwalled carbon nanotubes (MWCNTs) as a highly reversible anode material for high-performance lithium-ion batteries. Galvanostatic charge/discharge, cyclic voltammograms(CVs) and electrochemical impedance spectra (EIS) testing results indicate that the Co₂SnO₄–MWCNTs composite display large reversible capacity, excellent cyclic performance and good rate performance, highlighting the importance of the added MWCNTs for maximum utilization of electrochemically active Co₂SnO₄ nanoparticles for energy storage applications in high-performance lithium-ion batteries.     

A novel and facile route of ink-jet printing to thin film SnO2 anode for rechargeable lithium ion batteries

Thin film SnO₂ electrode has been prepared for the first time by using a novel facile and low-cost ink-jet printing technique. Wet ball-milling was employed to stabilize SnO₂ nano particles and conducting agent acetylene black (AB) using two kinds of polymeric hyperdispersants CH10B and CH12B, respectively, to prepare the stable colloid as “ink”. The morphology, structure, composition and electrochemical performance of SnO₂ thin film electrodes were investigated in detail by SEM, TEM, XRD, EDX, cyclic voltammograms (CV) and galvanostatic charge-discharge measurements. SEM images show uniform distribution of as-printed SnO₂ thin film electrodes. The thickness of monolayer thin film electrode was about 770-780 nm by TEM observation. The thickness of SnO₂ thin film could be increased by repeating the printing procedure on the Cu foil substrate. The average thickness of 10-layer SnO₂ thin-film electrode after compression for electrochemical measurement was about 2.3 μm. High initial discharge capacity about 812.7 mAh/g was observed at a constant discharge current density of 33 μA/cm² in a potential range of 0.05-1.2 V. It is expected that ink-jet printing is a very feasible, simple, convenient and inexpensive way to prepare thin film electrode for lithium ion batteries.     

Nonaqueous and template-free synthesis of Sb doped SnO2 microspheres and their application to lithium-ion battery anode

Antimony doped SnO₂ (ATO) microspheres composed of ATO nanoparticles were prepared by using a hydrothermal process in a nonaqueous and template-free solution from the inorganic precursors (SnCl₄ and Sb(OC₂H₅)₃). The physical properties of the as-synthesized samples were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms, and X-ray photoelectron spectrum (XPS). The resulting particles were highly crystalline ATO microspheres in the diameter range of 3-10 μm and with many pores. The as-prepared samples were used as negative materials for lithium-ion battery, whose charge-discharge properties, cyclic voltammetry, and cycle performance were examined. The results showed that a high initial discharge capacity of 1981 mAh g⁻¹ and a charge capacity of 957 mAh g⁻¹ in a potential range of 0.005-3.0 V was achieved, which suggests that tin oxide-based materials work as high capacity anodes for lithium-ion rechargeable batteries. The cycle performance is improved because the conducting ATO nanoparticles can also perform as a better matrix for lithium-ion battery anode.     

Synthesis and structural characterization of layered Li[Ni1/3Co1/3Mn1/3]O2 cathode materials by ultrasonic spray pyrolysis method

The layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ materials were synthesized by a spray pyrolysis method using citric acid as a polymeric agent. The Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and high-resolution transmission electron microscopy (TEM). The discharge capacity increases linearly with the increase of the upper cut-off voltage limit. TEM analysis showed that particles in the as-prepared powder possessed a polycrystalline structure. During cycling, the particle structure is mostly preserved although some surface grains on the polycrystalline particle became separated and transformed to the spinel phase.     

Facile synthesis and superior anodic performance of ultrafine SnO2-containing nanocomposites

Ultrafine SnO₂-containing nanocomposites were synthesized from glucose/SnCl₂ acid solution under hydrothermal environment. The content of SnO₂ in the nanocomposites could be adjusted by changing the mass ratio of SnCl₂ to glucose in the initial solution. The crystalline structure and morphology of the as-synthesized nanocomposites have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results revealed that the nanocomposites were composed of highly dispersing SnO₂ nanoparticles with the sizes of only a few nanometers (3–5 nm). Electrochemical tests demonstrated that the electrochemical performances were strongly dependent on the content of SnO₂ in the nanocomposites. The nanocomposites containing 75 wt.% SnO₂ exhibited an outstanding reversible capacity of 610 mAh/g and high capacity retention after 200 cycles. The extraordinary performance should originate from the very small size of SnO₂ nanoparticles and carbon precursor matrix derived from glucose which can confer the ability to accommodate the volume changes and prevent the agglomeration of Sn particles during charge/discharge process.     

Tin oxide nanosensor fabrication using AC dielectrophoretic manipulation of nanobelts

Nanobelts are a new class of semiconducting metal oxide nanowires. The ribbon-like nanobelts are chemically pure and structurally uniform single crystals, with clean, sharp, smooth surfaces, and rectangular cross-sections. Positive and negative dielectrophoresis (DEP) was demonstrated for the first time on semiconducting oxide nanobelts. This effect was then used for the fabrication of a nanodevice, which consisted of SnO₂ nanobelts attached to castellated gold electrodes defined on a glass substrate, and covered by a microchannel. The SnO₂ nanobelts (width ∼ 100-300 nm, thickness ∼ 30-40 nm) were suspended in ethanol and introduced into the microchannel. An alternating (AC) voltage of ∼9.8 V peak to peak, with variable frequency, was applied between the electrodes (minimum electrode gap ∼ 20 μm), which corresponds to an average electric field strength of less than 2.5 × 10⁵ V/m. In the 10 Hz-1 kHz range, repulsion between the nanobelts and the electrodes occurred, while in the 1-10 MHz range, attraction was observed. Once the nanobelts touched the electrodes, those that were sufficiently long bridged the electrode gaps. The device was characterized and can potentially be used as a nanosensor.     

Effect of hydrogen treatment on the porous structure of Al2O3-SnO2 system

The results of an investigation of the porous structure of the Al₂O₃-SnO₂ system and its properties after hydrogen treatment are presented. Pore size distribution was determined on the basis of low temperature nitrogen adsorption measurements. Reduction of the system by H₂ leads to a decrease of the parameters defining porous structure. We conclude that this is due to the reduction of Sn(IV) species to oxidation state II.     

Microwave dielectric properties of neodymium tin oxide

The microwave dielectric properties of Nd₂Sn₂O₇ ceramics were investigated with a view to their application in mobile communication. Nd₂Sn₂O₇ ceramics were prepared by the conventional solid-state method with various sintering durations. A maximum density of 7.11 g/cm³, a dielectric constant (_εr${\epsilon }_r$) of 17.02, a quality factor (Qf) of 33,100 GHz, and a temperature coefficient of resonant frequency (_τf${\tau }_f$) of −55 ppm/°C were obtained when Nd₂Sn₂O₇ ceramics were sintered at 1550 °C for 9 h.     

Synthesis of mesoporous SnO2 spheres via self-assembly and superior lithium storage properties

This paper firstly reported a simple route to prepare SnO₂ mesoporous spheres for lithium ion battery. Mesoporous SnO₂ spheres in range of 100–300 nm were prepared by primary reaction at 353 K for 30 min, and calcination process at 773 K, which could be scaled up for manufacturing. The nano-size effect of the small particle and the 3D mesoporous structure promoted the electrolyte and lithium ion transfer and suppressed the volume changes, which greatly enhanced the cycle performances. As the anode material, it could deliver 761 mAh g⁻¹ capacity after 50 cycles at the current density of 200 mA g⁻¹. Even at 2 A g⁻¹, it retained 480 mAh g⁻¹ after 50 cycles. Furthermore, we suggested that the high stability of the structure was responsible for the improved cycle properties.