Synthesis of Li₂Ti₃O₇ Anode Materials by Ultrasonic Spray Pyrolysis and Their Electrochemical Properties.
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ABSTRACT: Ramsdellite-type lithium titanate (Li₂Ti₃O₇) powders were synthesized by performing ultrasonic spray pyrolysis, and their chemical and physical properties were characterized by performing Scanning Electron Microscope (SEM), powder X-ray Diffraction (XRD), and Inductively Coupled Plasma (ICP) analyses. The as-prepared Li₂Ti₃O₇ precursor powders had spherical morphologies with hollow microstructures, but an irregularly shaped morphology was obtained after calcination above 900 °C. The ramsdellite Li₂Ti₃O₇ crystal phase was obtained after the calcination at 1100 °C under an argon/hydrogen atmosphere. The first rechargeable capacity of the Li₂Ti₃O₇ anode material was 168 mAh/g at 0.1 C and 82 mAh/g at 20 C, and the discharge capacity retention ratio was 99% at 1 C after the 500th cycle. The cycle performance of the Li₂Ti₃O₇ anode was also highly stable at 50 °C, demonstrating the superiority of Li₂Ti₃O₇ anode materials reported previously.
Project description:CuZnO (CZO) films have attracted increasing amounts of attention due to their promising potential applications in semiconductor devices. ZnO shows n-type conductivity, and attempts have been made to dope several elements in ZnO to improve the electrical properties. This study investigated the electrical property transitions of CZO films and determined the copper concentration at which the conductivity of CZO films will change from n-type to p-type. In this study, CZO films were fabricated by ultrasonic spray pyrolysis with copper acetate, zinc acetate, and ammonium acetate precursor solution. The concentrations of Cu ions in the CZO films were controlled by the concentration ratios of copper acetate to zinc acetate in the precursor solutions. In addition, these samples were analyzed by Hall effect measurements, X-ray diffraction, transmittance measurements, and photoluminescence measurements. The results show that the conductivity of the CZO film changes from n-type to p-type when the copper ion concentration in the film is 5%.
Project description:Tungsten sulfide (WS2)-carbon composite powders with superior electrochemical properties are prepared by a two-step process. WO3-carbon composite powders were first prepared by conventional spray pyrolysis, and they were then sulfidated to form WS2-carbon powders. Bare WS2 powders are also prepared by sulfidation of bare WO3 powders obtained by spray pyrolysis. Stacked graphitic layers could not be found in the bare WS2 and WS2-carbon composite powders. The amorphous bare WS2 and WS2-carbon composite powders have Brunauer-Emmett-Teller (BET) surface areas of 2.8 and 4 m(2) g(-1), respectively. The initial discharge and charge capacities of the WS2-carbon composite powders at a current density of 100 mA g(-1) are 1055 and 714 mA h g(-1), respectively, and the corresponding initial Coulombic efficiency is 68%. On the other hand, the initial discharge and charge capacities of the bare WS2 powders are 514 and 346 mA h g(-1), respectively. The discharge capacities of the WS2-carbon composite powders for the 2(nd) and 50(th) cycles are 716 and 555 mA h g(-1), respectively, and the corresponding capacity retention measured after first cycle is 78%.
Project description:Tungsten oxide (WO₃) is prepared by a low-temperature ultrasonic spray pyrolysis method in air atmosphere, and it is used as an anode buffer layer (ABL) for organic solar cells (OSCs). The properties of the WO₃ transition metal oxide material as well as the mechanism of ultrasonic spray pyrolysis processes are investigated. The results show that the ultrasonic spray pyrolysized WO₃ ABL exhibits low roughness, matched energy level, and high conductivity, which results in high charge transport efficiency and suppressive recombination in OSCs. As a result, compared to the OSCs based on vacuum thermal evaporated WO₃, a higher power conversion efficiency of 3.63% is reached with low-temperature ultrasonic spray pyrolysized WO₃ ABL. Furthermore, the mostly spray-coated OSCs with large area was fabricated, which has a power conversion efficiency of ~1%. This work significantly enhances our understanding of the preparation and application of low temperature-processed WO₃, and highlights the potential of large area, all spray coated OSCs for sustainable commercial fabrication.
Project description:Si-based anodes for Li-ion batteries (LIBs) are considered to be an attractive alternative to graphite due to their higher capacity, but they have low electrical conductivity and degrade mechanically during cycling. In the current study, we report on a mass-producible porous Si-CoSi2-C composite as a high-capacity anode material for LIBs. The composite was synthesized with two-step milling followed by a simple chemical etching process. The material conversion and porous structure were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy. The electrochemical test results demonstrated that the Si-CoSi2-C composite electrode exhibits greatly improved cycle and rate performance compared with conventional Si-C composite electrodes. These results can be ascribed to the role of CoSi2 and inside pores. The CoSi2 synthesized in situ during high-energy mechanical milling can be well attached to the Si; its conductive phase can increase electrical connection with the carbon matrix and the Cu current collectors; and it can accommodate Si volume changes during cycling. The proposed synthesis strategy can provide a facile and cost-effective method to produce Si-based materials for commercial LIB anodes.
Project description:The electrochemical performances of Li4Ti5O12 (LTO) and Li4Ti5O12-rutile TiO2 (LTO-RTO) composite electrodes at low temperatures were evaluated. The electrochemical performance of both electrodes decreased at low temperatures; regardless, the LTO-RTO electrode performed better than the LTO electrode. First, high viscosity and low ion conductivity of liquid electrolytes at low temperatures significantly reduce electrochemical performance. Second, cycling at low temperatures changes the crystal structure of LTO-based electrodes, impeding lithium ion diffusion and even causing the diffusion path to change from easy to difficult. However, changes in the crystal structure of the LTO-RTO electrode were not sufficient to change this path; thus, diffusion continued along the 8a-16c-8a pathway. Finally, from the perspective of dynamics, aggravation of a side reaction, increase in charge transfer resistance and polarization, and decrease in lithium ion diffusion at low temperatures reduce the electrochemical performance of LTO-based anode materials. However, the activation energy based on lithium ion diffusion is lower in the LTO-RTO electrode than the LTO electrode. The results confirmed that the electrochemical performance of the LTO-RTO electrode was better than that of the LTO electrode at low temperatures.
Project description:We report the synthesis of LiCoO2 (LCO) cathode materials for lithium-ion batteries via aerosol spray pyrolysis, focusing on the effect of synthesis temperatures from 600 to 1000 °C on the materials' structural and morphological features. Utilizing both nitrate and acetate metal precursors, we conducted a comprehensive analysis of material properties through X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Our findings reveal enhanced crystallinity and significant oxide decomposition within the examined temperature range. Morphologically, nitrate-derived particles exhibited hollow, spherical shapes, whereas acetate-derived particles were irregular. Guided by high-temperature X-ray diffraction (HT-XRD) data, the formation of a layered LCO oxide structure, with distinct spinel Li2Co2O4 and layered oxide LCO phases was shown to emerge at different annealing temperatures. Optimally annealed particles showcased well-defined layered structures, translating to high electrochemical performance. Specifically, nitrate-based particles annealed at 775 °C for 1 h demonstrated initial discharge capacities close to 179 mAh/g, while acetate-based particles, annealed at 750 °C for 3 h, achieved 136 mAh/g at a 0.1C discharge rate. This study elucidates the influence of synthesis conditions on LCO cathode material properties, offering insights that advance high throughput processes for lithium-ion battery materials synthesis.
Project description:A method of microalgae-templated spray drying to develop hierarchical porous Fe3O4/C composite microspheres as anode materials for Li-ion batteries was developed. During the spray-drying process, individual microalgae serve as building blocks of raspberry-like hollow microspheres via self-assembly. In the present study, microalgae-derived carbon matrices, naturally doped heteroatoms, and hierarchical porous structural features synergistically contributed to the high electrochemical performance of the Fe3O4/C composite microspheres, enabling a discharge capacity of 1375 mA·h·g-1 after 700 cycles at a current density of 1 A/g. Notably, the microalgal frameworks of the Fe3O4/C composite microspheres were maintained over the course of charge/discharge cycling, thus demonstrating the structural stability of the composite microspheres against pulverization. In contrast, the sample fabricated without microalgal templating showed significant capacity drops (up to ~40% of initial capacity) during the early cycles. Clearly, templating of microalgae endows anode materials with superior cycling stability.
Project description:Sn-based oxide materials as an anode of lithium ion batteries (LIBs) suffer from the unavoidable mechanical stress originated from huge volume changes during lithiation/delithiation reactions. We synthesized the hierarchical SnO nanobranches (NBs) decorated with Sn nanoparticles on Cu current collector using a vapor transport method. The Sn-decorated SnO NBs as an anode of LIB showed good electrochemical performance with high reversible capacity retention of as high as 502 mAh/g and rate capability of 455 mAh/g at a current density of 2.0 A/g after 50 cycles. Through the morphological and crystal structure analyses after the charge and discharge processes, it was found that the morphology of Sn-decorated SnO NBs was transformed to nanoporous layered-structure, composed of Sn and lithium oxide, during the repeated lithiation/delithiation reactions. The free-volume of Sn-decorated SnO NBs and nanoporous layered-structure effectively accommodate the huge volume changes and enhance the electrochemical cyclability by facilitating the diffusion of Li-ions.
Project description:Ordered mesoporous titania, prepared via low-temperature spray deposition, was examined as an anode material for lithium ion batteries. The material exhibits an exceptionally high electrochemical capacity of 680 mA h g-1 during the first discharge, which rapidly decreases over the following cycles. The capacity stabilizes at around 170 mA h g-1 after 50 cycles and the material delivers 83 mA h g-1 at high charge/discharge rates (10C). A combination of electrochemical and structural characterization techniques were used to study the charge/discharge behavior of the material and the origin of the irreversible capacity. To determine the effect of cycling on the structure of the material, X-ray absorption spectroscopy (XAS) and energy filtered TEM were carried out on pristine and cycled samples in intercalated and deintercalated states. Titanium K-edge XAS measurements showed that intercalated lithium affects the NEXAFS region. By comparing peak intensity ratios, we propose a method to quantify the amount of lithium inserted into the titania structure and to differentiate between lithium bound in close proximity to titanium, and lithium bound further away from titanium. Additionally, we suggest that the irreversible loss in capacity is due to the formation of phases that are stable, and thereby electrochemically inactive, over the electrochemical cycling conditions applied.
Project description:The use of cobalt hydroxychloride [Co2(OH)3Cl] as an anode material for lithium ion batteries (LIBs) is investigated using spherical shape and ultrafine nanocrystals directly formed by spray pyrolysis from spray solution of cobalt chloride salt. Dot-mapping images of the resulting powders reveal a uniform distribution of Co, O, and Cl throughout the powder. The Co2(OH)3Cl powder prepared directly by spray pyrolysis exhibits a high thermal stability at temperatures below 220 °C, as well as having superior electrochemical properties compared with those of the CoCl2(H2O)2 and CoO powders prepared by the same process. The initial discharge capacities of the Co2(OH)3Cl and CoO powders at a constant current density of 1000 mA g(-1) are found to be 1570 and 1142 mA h g(-1), respectively, and their initial Coulombic efficiencies are 72 and 70%. The discharge capacities of the Co2(OH)3Cl and CoO powders after 100 cycles are 955 and 632 mA h g(-1), respectively. The Co2(OH)3Cl powders have a high discharge capacity of 609 mA h g(-1) even after 1000 cycles at a high current density of 5000 mA g(-1).