Microstructural and electrochemical properties of Ti-doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coated LiCoO<Subscript>2</Subscript> films

We studied the microstructural and electrochemical properties of Ti-doped Al₂O₃ (Ti-Al₂O₃) coated LiCoO₂ thin films depending on the Ti composition. The 1.27 at.% Ti-Al₂O₃ coated films had an amorphous structure with better conductivity than that of pure Al₂O₃ films. The Ti-Al₂O₃ coating layer effectively suppressed the dissolution of Co and the formation of lower Li conductivity SEI films at the interface between the LiCoO₂ film and electrolyte. The Ti-Al₂O₃ coating improved the cycling performance and capacity retention at high voltage (4.5 V) of the LiCoO₂ films. The Ti-Al₂O₃ coated LiCoO₂ films showed better electrochemical properties than did the pure Al₂O₃ coated LiCoO₂ films. These results were closely related to the enhanced Li-conductivity and interfacial quality of the Ti-Al₂O₃ film.     

Dependence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coating thickness and annealing conditions on microstructural and electrochemical properties of LiCoO<Subscript>2</Subscript> film

We studied the dependence of Al₂O₃ coating thickness and annealing conditions on the surface morphology and electrochemical properties of Al₂O₃ coated LiCoO₂ films. The optimum coating thickness allowing for the highest capacity retention was about 24 nm. A sample consisting of Al₂O₃ coated on annealed LiCoO₂ film with additional annealing at 400 °C had a uniform coating layer between the coating materials and cathode films. This sample showed the best capacity retention of ∼91 % with a charge-cut off of 4.5 V after 30 cycles, while the bare cathode film showed a capacity retention of ∼32 % under the same conditions. The formation of second phases such as Co-Al-O was observed in the coating films by X-ray photoelectron spectroscopy (XPS). The Co-Al-O containing samples showed a higher initial capacity because of their smaller grain size, but less capacity retention than the Al₂O₃ containing samples.     

Effect of a surface treatment for LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> cathode material in lithium secondary batteries

LiNi_1/3Co_1/3Mn_1/3O₂ cathode material was surface-treated to improve its electrochemical performance. Al₂O₃ nanoparticles were coated onto the surface of LiNi_1/3Co_1/3Mn_1/3O₂ powder using a sol-gel method. The as-prepared Al₂O₃ nano-particle was identified as the cubic structure of Al₂O₃. XRD showed that the LiNi_1/3Co_1/3Mn_1/3O₂ structure was not affected by the Al₂O₃ coating. With a coating of 3 wt.% Al₂O₃ on LiNi_1/3Co_1/3Mn_1/3O₂, the cyclic-life performance and rate capability were improved. However, heavier coatings (5 wt.%) on LiNi_1/3Co_1/3Mn_1/3O₂ resulted in a considerable decrease of the discharge capacity and rate capability. The thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂ materials was greatly improved by the 3 wt.% Al₂O₃ coating.     

Electrochemical properties of spinel compound LiNi_（0.5）Mn_（1.2）Ti_（0.3）O_4 as cathode materials for lithium ion batteries

The electrochemical properties of spinel compound LiNi0.5Mn1.2Ti0.3O4 were investigated in this study.The chemicals LiAc·2H2O,Mn(Ac)2·2H2O,Ni(Ac)2·4H2O,and Ti(OCH3)4 were used to synthesize LiNi0.5Mn1.2Ti0.3O4 by a simple sol-gel method.The discharge capacity of the sample reached 134 mAh/g at a current rate of 0.1C.The first and fifth cycle voltammogram almost overlapped,which showed that the prepared sample LiNi0.5Mn1.2Ti0.3O4 had excellent good cycle performance.There were two oxidation peaks at 4.21 V and 4.86 V,and two reduction peaks at 4.55 V and 3.88 V in the cycle voltammogram,respectively.By electrochemical impedance spectroscopy and its fitted result,the lithium ion diffusion coefficient was measured to be approximately 7.76 × 10?11 cm2/s.     

Magnetic properties and crystallization kinetics of Zn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>

Precursor of nanocrystalline Zn0.5Ni0.5Fe2O4 was obtained by grinding mixture of ZnSO4·7H2O,NiSO4·6H2O,FeSO4·7H2O,and Na2CO3·10H2O under the condition of surfactant polyethylene glycol(PEG)-400 being present at room temperature,washing the mixture with water to remove soluble inorganic salts and drying it at 373 K.The spinel Zn0.5Ni0.5Fe2O4 was obtained via calcining precursor above 773 K.The precursor and its calcined products were characterized by differential scanning calorimetry(DSC) ,Fourier transform infrared(FT-IR) ,X-ray diffraction(XRD) ,and vibrating sample magnetometer(VSM) .The result showed that Zn0.5Ni0.5Fe2O4 obtained at 1073 K had a saturation magnetization of 74 A·m2·kg-1.Kinetics of the crystallization process of Zn0.5Ni0.5Fe2O4 was studied using DSC technique,and kinetic parameters were determined by Kissinger equation and Moynihan et al.equation.The value of the activation energy associated with the crystallization process of Zn0.5Ni0.5Fe2O4 is 220.89 kJ·mol-1.The average value of the Avrami exponent,n,is equal to 1.59±0.13,which suggests that crystallization process of Zn0.5Ni0.5Fe2O4 is the random nucleation and growth of nuclei reaction.     

LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles as cathode in aqueous lithium-ion battery

The aqueous lithium–ion batteries using LiMn₂O₄ as cathode materials are considered to be one of the most promising stationary power sources for large-scale energy storage devices. In the present work, LiMn₂O₄ nanoparticles were successfully synthesized by using sol-gel method, and the morphology of particles was characterized by SEM. We made three electrodes of this active material with PVDF binder and different conductive agents and another electrode of this active material with PTFE binder and Vulcan as a conductor. Electrochemical performances were tested in 5 M LiNO₃ aqueous electrolyte, and comparisons between these electrodes were accomplished.     

Synthesis and electrochemical performance of YF<Subscript>3</Subscript>-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode materials for Li-ion batteries

Spinel LiMn₂O₄ cathodes were coated with 1 mol% YF₃. X-ray diffraction (XRD) analyses showed that Y and/or F did not enter the lattice of the LiMn₂O₄ crystal. Transmission electron microscopy (TEM) showed that a compact YF₃ layer of 5–20 nm in thickness was coated onto the surface of LiMn₂O₄ particles. Scanning electron microscopy (SEM) observation showed that the YF₃ coating caused the agglomeration of LiMn₂O₄ particles. The cycling test demonstrated that the YF₃ coating can improve the electrochemical performance of LiMn₂O₄ at both 20 and 55°C. Moreover, YF₃-coated LiMn₂O₄ exhibited an improved rate capability compared with the uncoated one at high rates over 5C. The immersion test in electrolytes showed that YF₃-coated LiMn₂O₄ is more erosion resistant than the uncoated one.     

Synthesis and electrochemical performances of LiCoO<Subscript>2</Subscript> recycled from the incisors bound of Li-ion batteries

A new LiCoO₂ recovery technology for Li-ion batteries was studied in this paper. LiCoO₂ was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li₂CO₃, LiOH·H₂O and LiAc·2H₂O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO₂ was obtained by calcining the mixture at 850°C for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO₂ synthesized by adding Li₂CO₃ is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g⁻¹ between 3.0–4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g⁻¹.     

Corrosion and time dependent passivation of Al 5052 in the presence of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Corrosion and time–dependent oxide film growth on AA5052 Aluminum alloy in 0.25M Na₂SO₄ solution containing H₂O₂ was studied using electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometric and open circuit potential monitoring. It was found that sequential addition of H₂O₂ provokes passivation of AA5052 which ultimately thickens the oxide film and brings slower corrosion rates for AA5052. H2O2 facilitates kinetics of oxide film growth on AA 5052 at 25° and 60 °C which is indicative of formation of a thick barrier film that leads to an increment in the charge transfer resistance. Pitting incubation time increases by introduction of H₂O₂ accompanied by lower pitting and smoother surface morphologies. At short exposure (up to 8 h) to H₂O₂–containing solution, the inductive response at low frequencies predominantly determined the corrosion mechanism of AA5052. On the other hand, at prolonged exposure times (more than 24 h) to 0.25M Na₂SO₄+1vol% H₂O₂ solution, thicker oxide layers resulted in the mixed inductive–Warburg elements in the spectra.     

Surface modification of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> with Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> for lithium ion batteries

Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.     

Preparation and characterization of nanostructured Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sn<Subscript>0.5</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Nanostructured Bi₂Se₃ and Sn_0.5-Bi₂Se₃ were successfully synthesized by hydrothermal coreduction from SnCl₂·H₂O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). Bi₂Se₃ powders obtained at 180°C and 150°C consist of hexagonal flakes of 50–150 nm in side length and nanorods of 30–100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin irregular nanosheets with a size of 100–200 nm and several nanometers in thickness. The major phase of Sn_0.5-Bi₂Se₃ synthesized at 180°C is similar to that of Bi₂Se₃. Sn_0.5-Bi₂Se₃ powders are primarily nanorod structures, but small amount of powders demonstrate irregular morphologies.     

Thermodynamic Assessment of PrCl<Subscript>3</Subscript>-CaCl<Subscript>2</Subscript> and NdCl<Subscript>3</Subscript>-CaCl<Subscript>2</Subscript> Systems

By using the CALPHAD technique, an assessment of the binary PrCl₃-CaCl₂ and NdCl₃-CaCl₂ systems have been carried out. From measured phase equilibrium data and experimental integral properties, the PrCl₃-CaCl₂ and NdCl₃-CaCl₂ phase diagrams were optimized and calculated. A set of thermodynamic functions has been optimized based on an interactive computer-assisted analysis. The calculated results by present method agree well with the experimental data.     

Comparative analysis of the kinetics of dissolution of oxides Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> in the iron matrix upon mechanical alloying

The kinetics of low-temperature dissolution of oxides Y₂O₃ and Fe₂O₃ in an iron matrix during mechanical alloying has been studied using electron microscopy. It has been shown that the dissolution rate upon deformation of primary coarse oxides Fe₂O₃ in α iron (and, hence, saturation of the α matrix with oxygen) during treatment in a ball mill for up to 10 h is several times higher than the dissolution rate of Y₂O₃ oxides. The high-temperature (1100°C) annealing of a mechanoalloyed mixture of Fe + 1.5% Y + 1.35% Fe₂O₃ leads to the precipitation of 60% (of the total number of particles) secondary oxides 2–5 nm in size and only of 5–7% secondary nanooxides in a mechanoalloyed mixture of Fe + 2% Y₂O₃.     

Preparation and optical properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> powder

Y(NO3)3 and NH3·H2O were used as a raw materials,and nano-Y2O3 powder was successfully synthesized by a precipitation method.Employing TEOS as a raw material,SiO2 powder was successfully prepared by a alkoxide-hydrolysis method,and a Y2O3/SiO2 composite powder was obtained by coating.The Y2O3,SiO2,and Y2O3/SiO2 powders were characterized using X-ray diffraction(XRD),scanning electron microscopy(SEM),and Fourier transform infrared spectrophotometer(FT-IR);the Y2O3 and Y2O3/SiO2 powders were further examined ...     

Preparation of CuInSe<Subscript>2</Subscript> films by ultrasonic electrodeposition-selenization and the improvement of their surface morphology

The CuInSe₂ compound was prepared by selenization of Cu-In precursor, which was ultrasonic electrodeposited at constant current. CuInSe₂ films were compacted to improve surface morphology. The films were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). It is indicated that ideal stoichiometric CuInSe₂ films can be obtained by the selenization of Cu-In precursor deposited at a current density of 20 mA/cm². Single-phase CuInSe₂ is formed in the selenization process, and it exhibits preferred orientation along the (112) plane. The CuInSe₂ films with smooth surface can be obtained under the pressure of 500 MPa at 60°C.     

Up-Date of a Thermodynamic Database of the ZrO<Subscript>2</Subscript>-Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System for TBC Applications

The thermodynamic database of the ZrO₂-Gd₂O₃-Y₂O₃-Al₂O₃ system is up-dated taking into account new data on lattice stabilities of ZrO₂, Gd₂O₃ and Y₂O₃ and heat capacity measurements for the monoclinic phase Gd₄Al₂O₉ and phase with garnet structure Gd₃Al₅O₁₂. New data for the heat capacities of Gd₂Zr₂O₇ (pyrochlore) and GdAlO₃ (perovskite) as well as on the enthalpy of formation of fluorite solid solutions (Zr_1−x Gd _x )O_2−x/2 were found to be in good agreement with calculated results. In comparison with the previous assessment, taking into account new experimental data resulted in a change of the melting character of the Gd₄Al₂O₉ phase from a peritectic one to a congruent one in the Gd₂O₃-Al₂O₃ system. Correspondently, in the ternary system ZrO₂-Gd₂O₃-Al₂O₃, the melting character of the three-phase assemblage Gd₂O₃ (B), Gd₄Al₂O₉ and GdAlO₃ changed from eutectic to transition type U. The T ₀-lines for T/M and F/T diffusionless transformations and driving force of partitioning to equilibrium assemblage T + F were calculated in the ZrO₂-Gd₂O₃-Y₂O₃ system.     

Electrochemical properties of carbon-coated LiFePO<Subscript>4</Subscript> and LiFe<Subscript>0.98</Subscript>Mn<Subscript>0.02</Subscript>PO<Subscript>4</Subscript> cathode materials synthesized by solid-state reaction

Olivine structured LiFePO4/C (lithium iron phosphate) and Mn2+-doped LiFe0. 98Mn0. 024/C powders were synthesized by the solid-state reaction. The effects of manganese partial substitution and different carbon content coating on the surface of LiFePO4 were considered. The structures and electrochemical properties of the samples were measured by X-ray diffraction (XRD), cyclic voltammetry (CV), charge/discharge tests at different current densities, and electrochemical impedance spectroscopy (EIS). The electrochemical properties of LiFePO4 cathodes with x wt. ％ carbon coating (x=3, 7, 11, 15) at γ=0. 2C, 2C (1C=170 mAh·g-1) between 2. 5 and 4. 3 V were investigated. The measured results mean that the LiFePO4 with 7 wt. ％ carbon coating shows the best rate performance. The discharge capacity of LiFe0. 98Mn0. 02PO4/C composite is found to be 165 mAh·g 1 at a discharge rate, γ=0. 2C, and 105 mAh·g-1 at γ=2C, respectively. After 10cycles, the discharge capacity has rarely fallen, while that of the pristine LiFePO4/C cathode is 150 mAh·g-1 and 98 mAh·g-1 at γ=0. 2 and 2C, respectively. Compared to the discharge capacities of both electrodes above, the evident improvement of the electrochemical performance is observed, which is ascribed to the enhancement of the electronic conductivity and diffusion kinetics by carbon coating and Mn2+-substitution.     

Structure and electric property comparison between Ge nanoclusters embedded in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>

Metal-insulator-semiconductor (MIS) structures containing Ge nanocrystals embedded in both Al₂O₃ and ZrO₂/Al₂O₃ are fabricated by an ultra-high vacuum electron-beam evaporation method. Secondary ion mass spectroscopy (SIMS) results indicate that Ge embedded in Al₂O₃ diffuses towards the surface of the Al₂O₃ layer after annealing at 800°C in N₂ ambient for 30 min. Ge embedded in ZrO₂/Al₂O₃ is stable, thus inducing less leakage current. Capacitance voltage studies indicate that annealing can effectively passivate the negatively charged trapping centers. Memory effect of the Ge nanoclusters is verified by hysteresis in the C-V curves in the Al₂O₃/Ge+Al₂O₃/Al₂O₃ and ZrO₂/Ge+Al₂O₃/Al₂O₃ samples. This article is based on a presentation in “The 7th Korea-China Workshop On Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24–27, 2003.     

Fabrication and Properties of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> Composite Coatings

Al₂O₃ /xZrO₂ (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al₂O₃ and nano-sized monoclinic-ZrO₂ powders. Microstructural investigation showed that the coatings comprised well-separated Al₂O₃ and ZrO₂ lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al₂O₃ and tetragonal-ZrO₂ with trace of original α-Al₂O₃ and monoclinic-ZrO₂ phases. The effect of ZrO₂ addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO₂ improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.     

Phase Diagram of the Quaternary Al(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>-Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-Zn(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O System

The phase diagram of the H₂O-Zn(NO₃)₂-Al(NO₃)₃-Cu(NO₃)₂ quaternary system at 30 °C has been established by using the conductivity measurements. The solid-liquid equilibria of the H₂O-Zn(NO₃)₂-Al(NO₃)₃, H₂O-Zn(NO₃)₂-Cu(NO₃)₂, H₂O-Al(NO₃)₃-Cu(NO₃)₂ ternary systems and two isoplethic sections were determined experimentally. The solid phases in equilibrium with the saturated solution are the tri- and hemipentahydrate of copper nitrate, the hexahydrate α and β of the zinc nitrate and the nonahydrate of aluminum nitrate. The copper and zinc nitrates are relatively soluble in opposition to the aluminum nitrate which presents some important precipitation domains.