Preparation of LiFePO4/C composite powders by ultrasonic spray pyrolysis followed by heat treatment and their electrochemical properties

LiFePO₄ powders could be successfully prepared from a precursor solution, which was composed of Li(HCOO)·H₂O, FeCl₂·4H₂O and H₃PO₄ stoichiometrically dissolved in distilled water, by ultrasonic spray pyrolysis at 500 °C followed by heat treatment at sintering temperatures ranging from 500 to 800 °C in N₂ + 3% H₂ gas atmosphere. Raman spectroscopy revealed that α-Fe₂O₃ thin layers were formed on the surface of as-prepared LiFePO₄ powders during spray pyrolysis, and they disappeared after sintering above 600 °C. The LiFePO₄ powders prepared at 500 °C and then sintered at 600 °C exhibited a first discharge capacity of 100 mAh g⁻¹ at a 0.1 C charge-discharge rate. To improve the electrochemical properties of the LiFePO₄ powders, LiFePO₄/C composite powders with various amounts of citric acid added were prepared by the present method. The LiFePO₄/C (1.87 wt.%) composite powders prepared at 500 °C and then sintered at 800 °C exhibited first-discharge capacities of 140 mAh g⁻¹ at 0.1 C and 84 mAh g⁻¹ at 5 C with excellent cycle performance. In this study, the optimum amount of carbon for the LiFePO₄/C composite powders was 1.87 wt.%. From the cyclic voltammetry (CV) and AC impedance spectroscopy measurements, the effects of carbon addition on the electrochemical properties of LiFePO₄ powders were also discussed.     

Preparation of carbon coated ceramic foams by pyrolysis of polyurethane

Electronically conducting carbon coatings over alumina foams were prepared by the foams’ impregnation in a polyurethane solution, followed by pyrolysis of the polymer layer. An optimal coating procedure was developed, using a commercial polyurethane lacquer. Pyrolysis was performed by heating the coated foams to 650–1,200 °C in Argon for 2–8 h. Coating characterization included surface area, phase composition, morphological and electrical conductivity measurements. Auger electron spectroscopy (AES) showed the composition was mostly carbon, with trace levels of oxygen impurities. Thickness, microstructure and interface between the alumina foam surface and the carbon film were analyzed using scanning electron microscopy (SEM and HR-SEM).The carbon film’s specific electrical resistivity was 1–10 (Ω m×10⁻²), depending on the pyrolysis time, temperature and number of coatings. The resistivity was found to decrease by a factor of six when the pyrolysis temperature was increased from 750 to 1,200 °C. A second carbon layer, reduced the resistivity further by about a factor of two. These effects are attributed to densification, improved connectivity between the carbon grains and an overall thickening of the carbon layer. Thermal analysis and Raman measurements on the carbon films point to a grain rearrangement that is consistent with the improved conductivity of the films.     

Combustion characteristics of the heat pellet prepared from the Fe powders obtained by spray pyrolysis

Fe powders for thermal batteries were prepared by reduction of iron oxide powders obtained by spray pyrolysis. The iron oxide powders prepared by spray pyrolysis had fine size, spherical shape and high surface area. The morphologies of the Fe powders were affected by the preparation temperatures of the iron oxide powders. The Fe powders obtained from the iron oxide powders prepared by spray pyrolysis at 900 and 1000 °C had slightly aggregated structure of the primary powders with several microns sizes. The powders had pure Fe phases at reducing temperatures between 600 and 800 °C. The heat pellets with diameter of 18.2 mm were prepared using Fe powders and potassium perchlorate (KClO₄). The porosity of the prepared heat pellet was about 40%. The break strength of the heat pellet was 0.9 kgf. The ignition sensitivity of the heat pellet was 4 W. The maximum burn rate of the heat pellet obtained from the Fe powders were 8.6 cm s^?1.     

The production of ultrafine zirconium oxide powders by spray pyrolysis

Twin-fluid atomisation spray-pyrolysis has been investigated for the production of ZrO₂ powders. The atomiser used in this study has a novel internal arrangement that can produce a spray with a mean diameter (SMD) of less than 5 m. Spray pyrolysis tests with zirconium nitrate as a precursor salt were performed and the formation of ZrO₂ powder was studied under substantially different heating rates and initial solution concentrations. A mean particle diameter, d(0.5), of 0.67 m and 0.77 m was achieved for 0.05 M and 0.5 M solutions, respectively. It was concluded that the new nozzle design performed well and was successful in producing ultra-fine ZrO₂ powder with a principally tetragonal structure when the correct process conditions of heating rate and residence time were applied.     

Preparation of spherical Pb(Zr,Ti)O3 powders by ultrasonic spray pyrolysis

Spherical Pb(Zr,Ti)O₃ powders were prepared from the aqueous acetate-base solution by ultrasonic spray pyrolysis. The raw materials were Pb(C₂H₃O₂)-3H₂O, ZrO(C₂H₃O₂)₂ and a mixture of Ti(C₃H₇O)₄ and C₅H₇O₂. A single-phase PZT was formed at 900 C in air and at 700 C in O₂ atmosphere. The PbTiO₃ phase, as an intermediate product, was observed in the formation of PZT and no PbZrO₃ phase was detected under our experimental conditions. The intensity of the PbTiO₃ peak decreased with increasing reaction temperature in air, while the reverse effect of reaction temperature was observed in O₂. Spherical and irregular-shaped particles coexisted in the powder containing the minor PbTiO₃ phase, while the particles of a single-phase PZT have spherical morphology with little evidence of irregular-shaped particle formation.     

Preparation of ceria films by spray pyrolysis method

The deposition of CeO₂ films on fused-silica substrates by spray pyrolysis of a water–ethanol solution of a cerium nitrate precursor has been studied. Polycrystalline films have been obtained at a substrate temperature of 300–450°C after annealing of the deposit in air at temperatures in the range 350–500°C. It has been established that the best uniform ceria films with nanometric scale grains are prepared at a substrate temperature of 400°C with 0.5 h annealing of the deposit at 500°C. At lower spraying temperatures large CeO₂ crystallites have been observed on the film surface along with the fine grains. When the substrate temperature exceeds 400°C, numerous cracks caused by thermal stresses appear in the films.     

In-situ fabrication of nanostructured cobalt oxide powders by spray pyrolysis technique

Nano-crystalline Co3O4 and CoO powders have been prepared by a spray pyrolysis approach. The effects of the reaction temperature and initial salts on the crystallinity and phase composition have been studied. Based on the TEM and XRD results, the crystal sizes were in the range of 1-10 nm. SEM and TEM observations also reveal that the nano-powders easily create micron-scale spherical agglomerates. The Co3O4 powders obtained by spraying nitrate solution at 500 degrees C show high specific surface area, which according to the BET method is 82.37 m2/g. The time/temperature phase diagram of cobalt oxides developed from XRD and DTA/TGA analyses shows the existence of a CoO phase at low and high temperature ranges when some specific preparation conditions are applied.     

Preparation of spherical TiO2/SnO2 powders by ultrasonic spray pyrolysis and its spinodal decomposition

Spherical TiO₂/SnO₂ powders were prepared from the TiCl₄-SnCl₄ aqueous solution by ultrasonic spray pyrolysis. The particle size, particle-size distribution and morphology of the powders were studied in relation to concentration of source solutions and reaction temperatures. The width of the compositional undulation induced by spinodal decomposition in the sintered bodies increased with increasing starting particle sizes, which resulted from micro-compositional heterogeneity in the form of a solid solution within a TiO₂/SnO₂ secondary sphere.     

Preparation of coated iron powders by chemical plating

Small iron particles can be produced by reduction of γ-Fe2O3and α-FeOOH with hydrogen; they show outstanding magnetic properties and can be used for recording media. The main difficulty concerns the tendency of these particles to oxidize. We have studied a preparation process in two steps: a) reduction of iron oxides or oxy-hydroxides; b) chemical plating in the same furnace. The magnetic properties of the iron powders chiefly depend on the reduction step. The water content in the gas leaving the furnace has been shown to be the main parameter determining the obtainment of powders with high magnetic properties. The iron powders, which were pyrophoric, have been quenched in chemical plating bath of suitable formulation and coated with cobalt or copper. Typical magnetic properties are: saturation magnetization σsat= 130-165 emu/g, intrinsic coercivityjHc= 350-450 Oe; best magnetic properties: σsat=155 emu/g,jHc=700 Oe. The coated powders have been submitted to heat treatment in air saturated with water, showing a good resistance to oxidation.     

Synthesis and sintering of barium titanate fine powders by ultrasonic spray pyrolysis

Crystalline, spherical barium titanate fine powders with a narrow particle size distribution were prepared by ultrasonic spray pyrolysis. The stability of the starting solution was influenced by type of barium source and peptizer. The particle structure was influenced by the pyrolysis temperature of the barium source. The particle structure derived from barium acetate was dense, while powders derived from barium nitrate involved a lot of hollow particles. As-prepared powders were crystallized to a perovskite structure. Inductively coupled plasma analysis showed that the BaO/TiO₂ molar ratio of as-prepared powders was 50.5:49.5. The effects of the concentration of the starting fluid, pyrolysis temperature and flow rate of carrier air through the furnace on powder characteristics such as particle size, size distribution and crystal phase were investigated. The particle size depended on the concentration of starting solution and the flow rate of carrier air, but the particle size distribution was independent of these variables. Single-phase BaTiO₃ was obtained at more than 700°C. The relative density of barium titanate sintered at 1200°C was 98%. The hollow particles in the powders resulted in a low sintering density and a large grain size. The dielectric constant and tan δ of barium titanate at 25°C were 4500 and 0.02, respectively.     

Preparation of BaTiO3 nanoparticles by combustion spray pyrolysis

BaTiO₃ nanoparticles were synthesized by combustion spray pyrolysis using a 1:1 molar ratio of oxidizer and fuel. To prepare solution precursor, Ba(NO₃)₂, TiO(NO₃)₂, CH₆N₄O, and NH₄NO₃ with the molar ratio of 1:1:4:2.75 were mixed in distilled water with 10% ethyl alcohol. A 0.01 M solution was ultrasonically sprayed into a quartz tube heated at 800 °C. The number concentration of droplets was decreased and large particles were removed by passing the droplets through a metal screen filter. The synthesized particles were well crystallized tetragonal BaTiO₃. The median diameter of BaTiO₃ was 60 nm.     

Preparation of spherical Zr0.8Sn0.2TiO4 powder by ultrasonic spray pyrolysis

Fine, spherical Zr_0.8Sn_0.2Tio₄ powders were prepared by spray pyrolysis, using an ultrasonic transducer, from an aqueous solution of metal chlorides. The synthesized powders had a spherical morphology and many shell fragments. The observed shell fragments were attributed to the impermeable surface crust formed during thermal decomposition of the droplets. The raw materials for the preparation of Zr_0.8Sn_0.2TiO₄ were analysed prior to any treatments because the properties of the surface crust could be related to those of the raw materials. ZrOCl₂·8H₂O was supposed to affect the shell fragments as well. Spherical Zr_0.8Sn_0.2TiO₄ powders without shell fragments could be prepared using ZrO(CH₃COO)₂ in place of ZrOCl₂·8H₂O.     

Synthesis and formation mechanism of submicrometre spherical cordierite powders by ultrasonic spray pyrolysis

Cordierite powders containing very pure submicrometre spherical particles have been synthesized by the ultrasonic spray pyrolysis. Aqueous solutions of silicic acid, Al(NO3)3·9H2O and MgCl2·6H2O were used as precursors. Scanning electron micrographs have shown that particle surfaces were smooth and the mean particle diameter was 0.834 m. For the estimation of chemical and phase composition and phase transformation temperatures, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, energy dispersive spectroscopy and infrared analysis have been applied. It was found that during spray pyrolysis, the condensation of silicic acid mostly occurred while aluminium and magnesium ion remained incorported between Si–O–Si chains. By subsequent heating to over 800°C, Si–O–M bonds (M=Al, Mg) were formed. The synthesis of cordierite occurred by the crystallization of -cordierite from the amorphous phase at 900°C followed by the phase transformation of - into -cordierite in the temperature range 1100–1200°C.     

Preparation of nanocrystalline TiN coated cubic boron nitride powders by a sol-gel process

Cubic boron nitride (cBN) particles coated with 20 wt% nanocrystalline TiN were prepared by coating the surface of cBN particles with TiO2, followed by nitridation with NH3 gas at 900 degrees C. Coating of TiO2 on cBN powders was accomplished by a sol-gel process from a solution of titanium (IV) isopropoxide and anhydrous ethanol. An amorphous TiO(x) layer of 50 nm thickness was homogenously formed on the surface of the cBN particles by the sol-gel process. The amorphous layer was then crystallized to an anatase TiO2 phase through calcination in air at 400 degrees C. The crystallized TiO2 layer was 50 nm in thickness, and the size of TiO2 particles comprising the layer was nearly 10 nm. The TiO2 on cBN surfaces was completely converted into nanocrystalline TiN of uniform particles 20 nm in size on cBN particles by nitridation under flowing NH3 gas.     

Synthesis of submicron carbon spheres by the ultrasonic spray pyrolysis method

Submicron carbon spherical particles were obtained by polycondensation of resorcinol and formaldehyde in a solution and subsequent ultrasonic spray pyrolysis of the prepared sol. Microscopic characterization indicates the regular spherical shape of the obtained particles and sphere diameters in 200-700 nm range. The carbon spheres are amorphous as confirmed by electron diffraction, EELS, XRD and HREM characterization. Activation procedure was performed with H₂O in a nitrogen flow for 15 and 30 min at 800 °C. The activation procedure preserved the initial spherical shapes of the particles while the particle porosity and specific surface area were increased. The amount of surface oxygen functionalities was also increased by activation procedure as indicated by FTIR analysis.     

Low substrate temperature synthesis of carbon nanowalls by ultrasonic spray pyrolysis

In this paper, we report the synthesis of two-dimensional wall like carbon nanostructures (i.e. carbon nanowalls) by ultrasonic spray pyrolysis of ethanol and fullerene mixture. At higher temperature carbon nanofibers were formed on the substrate placed at the center of the reactor tube, whereas carbon nanowalls were observed on the substrate placed downstream of the tube below 100 °C. Spaces between the nanowalls changed with distance of the substrates from the furnace. Qualitative analysis of materials was performed using scanning electron microscopy, transmission electron microscopy and Raman spectroscopy.     

喷雾热解法在硅衬底上生长定向碳纳米管阵列(英文)

以向日葵油的甲基酯为碳源,二茂铁为催化剂前驱体,Ar为载气,通过喷雾热解法在硅衬底上合成定向碳纳米管阵列。结果表明,在硅衬底上原位形成Fe催化剂纳米颗粒。由拉曼光谱、透射电镜图和X-射线衍射谱图显示所制定向碳纳米管阵列具有较好的石墨化程度,其直径为1 0～3 0 nm,管壁约为1 0 nm。所制定向碳纳米管阵列中残留的催化剂含量可以忽略。     

己烷低耗喷雾热解法大规模制备多壁碳纳米管

以己烷为碳源,二茂铁为催化剂前躯体,应用喷雾热解法,制备了多壁碳纳米管(MWCNTs).采用酸沥滤和空气氧化对MWCNTs进行纯化.利用SEM、TEM、XRD、EDS、TGA及Raman光谱分析等方法分别对原生和纯化MWCNTs进行表征.为制得优质、高产MWCNTs,对制备工艺参数作了优选,分别研讨了最佳制备参数,包括:二茂铁升华温度、己烷中二茂铁浓度、热解温度和时间,己烷与H2的流量比.MWCNTs具有典型的腊肠状(Sawsage-like)构型,长度大于数十微米,内、外管径分别为15nm～45nm及25nm～70nm,MWCNTs的纯度和产率的质量分数分别高于95%和70%.