Al2O3/CrAlSiN multilayer coating deposited using hybrid magnetron sputtering and atomic layer deposition

In this study, Al₂O₃/CrAlSiN multilayer coatings with various periods were prepared using a hybrid process involving overlapping magnetron sputtering of CrAlSiN and atomic layer deposition (ALD) of Al₂O₃. The influence of the number of Al₂O₃ layers on the mechanical properties, corrosion behavior and oxidation characteristics of the coatings was studied using nano/micro indentation, electrochemical corrosion, and high temperature static oxidation tests. The results show that the multilayer structure can effectively prevent crack propagation during the coating and subsequently increase the coating toughness. A substantial improvement in the resistance to electrochemical and oxidation corrosion was observed in the Al₂O₃/CrAlSiN multilayer coatings and increasing the number of Al₂O₃ layers dramatically increases the corrosion durability. The Al₂O₃ ALD layers are expected to inhibit the diffusion of corrosive substances such as ions and oxygen and the increase of the Al₂O₃ layer number decreases the diffusion fluxes of the coating elements to the surface and limit the oxide growth, resulting in the evolution of the oxidation produces from irregular particles to nano-walls/fibers. It is supposed that the PVD/ALD hybrid process may open a new hard coating design concept by providing a superior toughness and corrosion/oxidation resistance.     

Enhanced cycleability of LiMn2O4 cathodes by atomic layer deposition of nanosized-thin Al2O3 coatings

This report is the first effort to use atomic layer deposition method for deposition of nanosized-thin and highly conformal Al(2)O(3) coatings onto LiMn(2)O(4) cathodes with precise thickness-control at atomic scale. The coated cathodes exhibit significantly enhanced cycleability than bare cathodes, as the dense ALD coating protects the cathode material from severe dissolution.     

Nanorod-like Fe2O3/graphene composite as a high-performance anode material for lithium ion batteries

In this study, a nanorod-like Fe₂O₃/graphene nanocomposite is synthesized by a facile template-free hydrothermal method and a following calcination in air at 300 °C for 2 h. The Fe₂O₃ nanorods with diameter of 15–30 nm and length of 120–300 nm are homogenous distributed on both sides of graphene. The morphologies of intermediates at different hydrothermal reaction times are investigated by transmission electron microscopy (TEM) characterization, and a possible growth mechanism of this one-dimensional structure is proposed. It is shown that the α-FeOOH rodlike precursors are formed through a rolling-broken-growth (RBG) model, then the α-FeOOH is transformed into α-Fe₂O₃ nanorods during calcinations, preserving the same rodlike morphology. Electrochemical characterizations demonstrate that the Fe₂O₃ nanorod/graphene composites exhibit a very large reversible capacity of 1063.2 mAh/g at the charge/discharge rate of 0.1 C.     

Effects of TiO2 starting materials on the synthesis of Li2ZnTi3O8 for lithium ion battery anode

Lithium zinc titanate (Li₂ZnTi₃O₈) anode materials have been successfully synthesized using rutile-TiO₂ with different particle sizes as titanium sources via a molten-salt method. Various physical and electrochemical methods are applied to characterize the effects of TiO₂ particle sizes on the structures and physicochemical properties of the Li₂ZnTi₃O₈ materials. When the particle size of TiO₂ is too small (10 nm), it is difficult to homogeneously mix TiO₂ with the other raw materials. Thus, the final product Li₂ZnTi₃O₈ has poor crystallinity, large particle size, small specific surface area, pore volume and average pore diameter, which are disadvantageous to its electrochemical performance. Using TiO₂ with the proper particle size of 100 nm as the titanium source, the Li₂ZnTi₃O₈ (R-100-LZTO) with excellent electrochemical performance can be obtained. At 1 A g⁻¹, 175.8 and 163.6 mA h g⁻¹ are delivered at the 1st and the 200th cycles, respectively. The largest capacities of 163, 133.3 and 122.5 mA h g⁻¹ are delivered at 2.5, 5 and 6 A g⁻¹, respectively. The good high-rate performance of the R-100-LZTO originates from the good crystallinity, small particle size, large specific surface area and average pore diameter, low charge-transfer resistance and high Li⁺ diffusion coefficient.     

Influence of argon plasma on the deposition of Al2O3 film onto the PET surfaces by atomic layer deposition

In this paper, polyethyleneterephthalate (PET) films with and without plasma pretreatment were modified by atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PA-ALD). It demonstrates that the Al₂O₃ films are successfully deposited onto the surface of PET films. The cracks formed on the deposited Al₂O₃ films in the ALD, plasma pretreated ALD, and PA-ALD were attributed to the energetic ion bombardment in plasmas. The surface wettability in terms of water contact angle shows that the deposited Al₂O₃ layer can enhance the wetting property of modified PET surface. Further characterizations of the Al₂O₃ films suggest that the elevated density of hydroxyl -OH group improve the initial growth of ALD deposition. Chemical composition of the Al₂O₃-coated PET film was characterized by X-ray photoelectron spectroscopy, which shows that the content of C 1s reduces with the growing of O 1s in the Al₂O₃-coated PET films, and the introduction of plasma in the ALD process helps the normal growth of Al₂O₃ on PET in PA-ALD.     

Designing carbon-supported Fe2O3 anodes for lithium ion batteries

Journal of Applied Electrochemistry - In this study, within the defined orthogonal array of Taguchi design, the hydrothermal process parameters have been optimized for fabricating the smallest...     

Simple fabrication of a Fe2O3/carbon composite for use in a high-performance lithium ion battery

A simple approach was developed for the fabrication of a Fe₂O₃/carbon composite by impregnating activated carbon with a ferric nitrate solution and calcinating it. The composite contains graphitic layers and 10 wt.% Fe₂O₃ particles of 20–50 nm in diameter. The composite has a high specific surface area of ∼828 m² g⁻¹ and when used as the anode in a lithium ion battery (LIB), it showed a reversible capacity of 623 mAh g⁻¹ for the first 100 cycles at 50 mA g⁻¹. A discharge capacity higher than 450 mAh g⁻¹ at 1000 mA g⁻¹ was recorded in rate performance testing. This highly improved reversible capacity and rate performance is attributed to the combination of (i) the formation of graphitic layers in the composite, which possibly improves the matrix electrical conductivity, (ii) the interconnected porous channels whose diameters ranges from the macro- to meso- pore, which increases lithium-ion mobility, and (iii) the Fe₂O₃ nanoparticles that facilitate the transport of electrons and shorten the distance for Li⁺ diffusion. This study provides a cost-effective, highly efficient means to fabricate materials which combine conducting carbon with nanoparticles of metal or metal oxide for the development of a high-performance LIB.     

SnO2 nanorods grown on graphite as a high-capacity anode material for lithium ion batteries

A novel architecture of SnO₂ nanorods grown on graphite has been synthesized by a simple hydrothermal method for lithium ion battery. The as-prepared products were characterized by XRD, FTIR, N₂ adsorption/desorption, FESEM and TEM. The electrochemical performances of SnO₂/graphite composite were measured by cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy. The results show that the SnO₂/graphite composite maintains high lithium storage capacity and good cycling stability, indicating its promising potential as a novel anode material for high-performance lithium ion batteries.     

Porous rod-shaped Co3O4 derived from Co-MOF-74 as high-performance anode materials for lithium ion batteries

Porous rod-shaped Co₃O₄ has been successfully synthesized by one-step thermal annealing of the as-prepared Co-MOF-74 precursor and tested as anode materials for lithium ion batteries. The porous rod-shaped Co₃O₄ is found to be very attractive for lithium-ion batteries. It demonstrates a reversible capacity of 683 mAh/g after 80 cycles at 100 mA/g and an excellent rate performance with high average discharge specific capacities of 1231, 1026, 733 and 502 mAh/g at 50, 100, 200 and 400 mA/g, respectively. The excellent electrochemical performance should be due to the porous structural and composition characteristics.     

Controllable synthesis of monodisperse ultrathin SnO(2) nanorods on nitrogen-doped graphene and its ultrahigh lithium storage properties

Monodisperse ultrathin SnO(2) nanorods on nitrogen-doped graphene were firstly synthesized by a facile one-step hydrothermal strategy. The uniformed composites with high nitrogen content and ultrathin SnO(2) nanorods of 2.5-4.0 nm in diameter and 10-15 nm in length show a high reversible specific capacity, superior rate capability and outstanding cycling stability (803 mA h g(-1)) as anode materials for lithium ion batteries, owing to the synergistic effect between GS and SnO(2) and nitrogen-doping, which can greatly decrease the energy barrier for Li penetrating the pyridinic defects and improve the electronic structures. This work opens the door to prepare metal oxide/GS-N composites with superior lithium storage properties and engineering of graphene composites for advanced energy storage.     

LiCo_(0.90)Al_(0.1)O_2的表面包覆及其性能研究

通过化学处理方法在LiCo0.90Al0.1O2的表面包覆后,在300℃下热处理6 h,得到表面包覆Al2O3的LiCo0.90Al0.1O2。SEM分析表明,包覆前表面光滑,包覆后可以明显看到晶粒表面粘有许多小颗粒。当充电到4.5 V时,包覆后的材料具有较好的充放电平台、较高的充放电容量和首次充放电效率,但是包覆后材料的首次充电容量有所下降。     

Porous Composite Ceramic Materials Produced by a Self-Propagating High-Temperature Synthesis in the Fe2O3 – Al2O3 – Al System

Mixtures of optimum composition for producing porous composite ceramic materials from industrial waste by the self-propagating high-temperature synthesis (SHS) are developed. A flowchart of the SHS process is proposed. Mixtures based on iron oxide and aluminum oxide with the addition of 8 wt.% powdered aluminum provide a route toward producing porous permeable materials from a waste of machine engineering (an alloy steel scale), competitive with materials produced by powder metallurgy techniques.     

Corrosion resistance of Al2O3-Y2O3-SiC coating on depleted uranium prepared by cathode plasma electrolytic deposition

Al₂O₃-Y₂O₃-SiC composite coatings were prepared on depleted uranium by cathode plasma electrolytic deposition in Al(NO₃)₃, Y(NO₃)₃, SiC nanoparticles and anhydrous ethyl alcohol mixture. The resulting coating consisted of an inner barrier layer and an outer porous layer. The SiC nanoparticles were incorporated into the composite coating and decreased the coating porosity by filling the pores. The potentiodynamic polarization test and neutral salt spray test revealed that the corrosion resistance of depleted uranium was enhanced by the composite coating. Moreover, with increasing the content of SiC nanoparticles in the coating, the coating corrosion resistance was improved gradually.     

An elastic carbon layer on echeveria-inspired SnO2 anode for long-cycle and high-rate lithium ion batteries

The commercialization of Sn-based anodes for lithium ion batteries is still hindered due to the inherent volume change leading to a rapid capacity fading during the electrochemical cycle. Inspired by echeveria, a plant that stores sufficient water in its hierarchical leaves to survive in a drought, we report a breakthrough by designing the hierarchical and nanoporous SnO₂ electrode encapsulated with ultrathin carbon layer (∼2 nm). As evidently captured by in situ transmission electron microscopy, the conformal carbon coating on the surface of anode may provide an elastic cover that suppresses the cracks due to severe volume change, and increases both electrical and ionic conductivity, allowing the cells to exhibit excellent lithium storage performance with more than 800 cycles even with relatively high-rate of current densities.     

Al2O3 films with Ni-Based buffer layer prepared by plasma-ion assisted deposition on Cu substrate

In this study, Al₂O₃ films with an Ni-based buffer layer were prepared on a Cu substrate by plasma-ion assisted deposition (PIAD). The main purpose of this study is to develop a novel electrical insulating film to be used at high temperature. X-ray diffraction (XRD) spectra show the Al₂O₃ films prepared by this method are amorphous. The results of atomic force microscopy (AFM), scanning electron microscopy (SEM), and auger electron spectroscopy (AES) analyses reveal that the Al₂O₃ films perfectly adhere to the substrate through the buffer layer, no visible defects were observed, and no impurity from Ni or Cu was detected. The diffusion of Cu into the Al₂O₃ film at high temperature is suppressed. Al₂O₃ films with an Ni-based buffer layer exhibit excellent resistivity (>10¹⁰Ω·cm) even after experiencing a high temperature environment as high as 600°C 10 times.     

Preparation of Al2O3 coating on TiN coating by polymer-assisted deposition to improve oxidation resistance in coking inhibition applications

In order to inhibit the metal catalytic coking and improve oxidation resistance of single TiN coating, the TiN/Al₂O₃ double layer coatings were designed as a chemically inert coating for methylcyclohexane supercritical pyrolysis. Internal TiN coatings were prepared by atmospheric pressure chemical vapor deposition using TiCl₄–H₂–N₂ system. The external Al₂O₃ coatings with different thicknesses were prepared on the TiN surface by polymer-assisted deposition, and the coating with the most suitable thickness was further annealed at different temperatures of 600, 700, 800 and 900 °C. The morphology, elemental and phase composition of TiN/Al₂O₃ coatings were characterized by SEM, EDX and XRD respectively. The chemical state information of the coating elements was based on Ti 2p, Al 2p core level X-ray photoelectron spectroscopy (XPS) spectra. The results indicated that the external Al₂O₃ coating will partially peel off at 900 °C annealing temperature. The thermogravimetric analysis results indicated that all TiN/Al₂O₃ coatings show better oxidation resistance than single-layer TiN coating. The anti-coking test with methylcyclohexane supercritical pyrolysis showed that the TiN/Al₂O₃ coatings can effectively cover the metal catalytic sites and eliminate metal catalytic coking. However, the acid sites of external Al₂O₃ coating slightly promoted coking, so the anti-coking ratios of TiN/Al₂O₃ coatings were smaller than that of TiN. Thus, the addition of external Al₂O₃ coating can greatly improve the oxidation resistance of TiN coatings with little loss of coking resistance.     

Preparation of Ni/Al2O3 catalysts from vapor phase by atomic layer epitaxy

Ni/Al₂O₃ catalysts were prepared by saturating gas-solid reactions as an atomic layer epitaxy (ALE) process. Vaporized Ni(acac)₂ was chemisorbed on a porous alumina support, and the produced surface complex was then air treated to remove the ligand residues. The nickel content could be precisely controlled by repeating this reactor cycle. On alumina preheated at 800°C, the nickel content varied from 3 to 21 wt%, when the number of reaction cycles was increased from one to ten. The performance of the Ni-catalysts was evaluated in the gas-phase hydrogenation of toluene. The preheat temperature of alumina influenced the activity of the catalyst, and a maximum in the activity was observed for catalysts prepared from alumina preheated at 875°C. Catalysts prepared by four reaction cycles, containing about 10 wt% nickel, gave the highest utilization of nickel.     

锂离子电池负极材料石墨碎除杂整形研究

以石墨电极副产物石墨碎为原料,分别对其进行了除杂与整形研究。除杂过程以浓盐酸为溶剂,采用水浴锅程序升温的方法;整形采用粉碎机粉碎。结果表明,在一定的反应时间和温度下,可达到较好的除杂效果;石墨碎整形后,呈现出圆整的球形或椭球形形貌,振实密度得到提高。     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Atomic layer deposition of Al2O3 on porous polypropylene hollow fibers for enhanced membrane performances

Porous polypropylene hollow fiber (PPHF) membranes are widely used in liquid purification.However,the hydrophobicity of polypropylene (PP) has limited its applications in water treatment.Herein,we demonstrate that,for the first time,atomic layer deposition (ALD) is an effective strategy to conveniently upgrade the filtration performances of PPHF membranes.The chemical and morphological changes of the deposited PPHF membranes are characterized by spectral,compositional,microscopic characterizations and protein adsorption measurements.Al2O3 is distributed along the cross section of the PP hollow fibers,with decreasing concentration from the outer surface to the inner surface.The pore size of the outer surface can be easily turned by altering the ALD cycles.Interestingly,the hollow fibers become much more ductile after deposition as their elongation at break is increased more than six times after deposition with 100 cycles.The deposited membranes show simultaneously enhanced water permeance and retention after deposition with moderate ALD cycle numbers.For instance,after 50 ALD cycles a 17％ increase in water permeance and one-fold increase in BSA rejection are observed.Moreover,the PP membranes exhibit improved fouling-resistance after ALD deposition.