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.     

Effect of the addition of Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> on the microstructure of laser cladding alloy coating layers

The effects on the microstructures and phases of coating layers by the addition of micron-sized (m) and nano-sized (n) (m&n) Sm₂O₃ powders were investigated. The coating materials, which were prepared by means of 2.0 kW CO₂ laser cladding, consist of a powder mixture of m Ni-based alloy (NBA) powders comprising 1.5 wt.% m Sm₂O₃ and 3.0% n Sm₂O₃ powders. The results indicate that γ-Ni, Cr₂₃C₆ and Ni₃B are the primary phases of the NBA coatings. The Fe₇Sm and Ni₃Si phases are highlighted by the addition of m&n Sm₂O₃ powders. From the substrate, planar crystal layers are first grown in all NBA and m&n Sm₂O₃/NBA coatings. The dendrite growth then occurs as a result of the addition of the m Sm₂O₃ powder, and the equiaxed dendrite growth occurs as a result of the addition of the n Sm₂O₃. With the addition of a rare earth oxide such as Sm₂O₃ powder, the width of the planar crystal becomes smaller than that of the NBA coating.     

Performance and capacity fading reason of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries after storing at high temperature

Spinel LiMn₂O₄ was synthesized by a solid-state method. A 204468-size battery was fabricated and stored at 55°C. The structure and morphology of the LiMn₂O₄ cathode were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. Energy dispersive spectroscopy (EDS) was used to analyze the surface component of the carbon anode. The discharge capacities of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 106, 98, 96, and 92 mAh·g⁻¹, respectively. The cyclic performance is improved after storage. The capacity retentions of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 83.8%, 85.8%, 86.9%, and 88.6% after 180 cycles. The intensity of all the LiMn₂O₄ diffraction peaks is weakened. Mn is detected from the carbon electrode when the battery is stored for 96 h. Cyclic voltammograms and electrochemical impedance spectroscopy (EIS) were used to examine the surface state of the electrode after storage. The results show that the resistance and polarization of LiMn₂O₄/electrolyte is increased after storage, which is responsible for the fading of capacity.     

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.     

Electrochemical properties of LiNi0.8Co0.2?xAlxO2 (0≤x≤0.1) cathode particles prepared by spray pyrolysis from the spray solutions with and without organic additives

Fine-sized LiNi_0.8Co_0.2−xAl_xO₂ (0≤x≤0.1) cathode particles were prepared by spray pyrolysis from the spray solutions with and without organic additives. Citric acid, ethylene glycol, and Drying Control Chemical Additive (DCCA) were used as organic additives and improved the morphologies and electrochemical properties of the cathode particles. The LiNi_0.8Co_0.2−xAl_xO₂ (0≤x≤0.1) cathode particles obtained from the spray solutions with organic additives were of micro size and had slightly aggregated morphologies. The initial discharge capacities of the LiNi_0.8Co_0.2−xAl_xO₂ (0≤x≤0.1) cathode particles obtained from the spray solutions without organic additive changed from 169 mAhg⁻¹ to 190 mAhg⁻¹ when the x changed from 0 to 0.1. However, the initial discharge capacities of the cathode particles obtained from the spray solutions with organic additives changed from 196 mAhg⁻¹ to 218 mAhg⁻¹. The initial discharge capacity of the LiNi_0.8Co_0.15Al_0.05O₂ cathode particles obtained from the spray solution with organic additives was maintained after the 20th cycle at a current density of 0.1 C.     

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.     

Tunneling magnetoresistance in sintered Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> samples diluted with Fe and α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Electric transport and magnetoresistance characteristics were investigated for Fe₃O₄-x Fe(x=0, 10, 20 wt.%) samples and Fe₃O₄-α-Fe₂O₃ samples sintered at 500°C. For composition dependence of Fe₃O₄-x Fe samples, the largest room temperature MR, 3.3% at 10 kOe, was obtained from a Fe₃O₄-10 Fe sample. For the surface heat treatment dependence of Fe₃O₄ powders, the largest room temperature MR, 4% at 10 kOe, was obtained from a Fe₃O₄-α-Fe₂O₃ sample sintered with Fe₃O₄ powders heated at 200°C in air. It was found that these enhanced MR ratios always appear together with the appropriate excess resistance which is regarded as the tunneling barrier. These enhanced MR ratios of Fe₃O₄-10 Fe and Fe₃O₄-α-Fe₂O₃ samples can be explained by the increased interparticle contact sites and the appropriate thickness of α-Fe₂O₃, respectively.     

导电Ti3O5包覆纳米铝粉的制备及其作为双离子电池负极材料的电化学性能研究

铝被认为是下一代电池最有前途的负极材料之一, 本文中采用导电的Ti₃O₅作为外壳包覆纳米铝粉来制备Al@Ti₃O₅核壳结构材料, 并将其作为负极材料应用到双离子电池(DIB)中。使用中间相炭微球(MCMB)作为正极材料,Al@Ti₃O₅作为负极材料制作Al@Ti₃O₅-MCMB双离子电池。电池的放电平台可达4.5V, 在电流倍率0.5C下(电流基于正极石墨的理论比容量计算,1C=372mAhg^_-1)放电比容量达到130.6mAhg^_-1,比能量密度为278.8Whkg^_-1。并且在高倍率5C下循环1000次过程中容量基本保持110mAhg^_-1不变,循环后容量保持率达到92.9%。     

Solvothermal synthesis and thermoelectric properties of skutterudite compound Fe（0.25）Ni（0.25）Co（0.5）Sb3

Nanostructured skutterudite-related compound Fe_0.25Ni_0.25Co_0.5Sb₃ was synthesized by a solvothermal method using FeCl₃, NiCl₂, CoCl₂, and SbCl₃ as the precursors and NaBH₄ as the reductant. The solvothermally synthesized powders consisted of fine granules with an average particle size of tens of nanometers. The bulk material was prepared by hot pressing the powders. Transport property measurements indicated a heavily doped semiconductor behavior with n-type conduction. The thermal conductivity is about 1.83 W·m⁻¹·K⁻¹ at room temperature and decreases to 1.57 W·m⁻¹·K⁻¹ at 673 K. The low thermal conductivity is attributed to small grain size and high porosity. A maximum dimensionless figure of merit of 0.15 is obtained at 673 K.     

Transport properties of Bi<Subscript>43</Subscript>Se<Subscript>4</Subscript>Te<Subscript>53</Subscript> thermoelectric alloy fabricated by mechanical grinding and pulse discharge sintering

Mechanical grinding followed by pulse discharge sintering was applied to fabricate n-type Bi₄₃Se₄Te₅₃ thermoelectric materials. Calorimetric measurements demonstrated that a Se-rich phase was developed from Bi₂(Se, Te)₃ phase after 10h of milling. However, when the milling time was extended to 25 h or longer, a Te-rich phase was formed. Hall measurements showed that the development of the Se/Te-rich phase considerably increased the carrier concentration but decreased the carrier mobility. The oxygen contamination in the smashed powders was also an important consideration for the degeneration of the figure of merit of the sintered samples.     

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.     

Electrochemical performance of C-La<Superscript>3+</Superscript> codoped LiFePO<Subscript>4</Subscript> synthesized by microwave heating

La³⁺ was selected to elevate the lattice electronic conductivity of LiFePO₄, and LiFePO₄/(C+La³⁺) cathode powders were synthesized by microwave heating using a domestic microwave oven for 35 min. The microstructures and morphologies of the synthesized materials were investigated by XRD and SEM. The electrochemical performances were evaluated by galvanostatic charge-discharge. The electrochemical performance of LiFePO₄ with different La³⁺ contents was studied. Results indicated that the initial specific discharge capacity of LiFePO₄/(C+La³⁺) composites with 2% La³⁺ (116.3 mAh/g) was better than that of LiFePO₄/C (105.4 mAh/g). The addition of La³⁺ further improved the electrochemical properties. So the codoping is an effective method to improve the electrochemical performance.     

Electromagnetic wave absorbing properties of Fe<Subscript>73</Subscript>Si<Subscript>16</Subscript>B<Subscript>7</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> base P/M sheets mixed with dielectric fine particles

Fe-based nanocrystalline powder sheets with dielectric TiO₂ powder additives were investigated to improve the characteristics of electromagnetic (EM) wave absorption. The amorphous ribbons of Fe₇₃Si₁₆B₇Nb₃Cu₁ (at.%) alloys were prepared by a planar flow casting (PFC) process, and the ribbons were pulverized using an attrition mill. Fe-based flake powder crystallized at 550°C for 1h was mixed with a nano-sized and a micro-sized TiO₂ powder. The powder mixtures were then tape-cast with binders to become EM wave-absorbing sheets. The absorbing properties of the fabricated sheet sample, such as complex permittivity and permeability, were measured by a network analyzer. The properties of EM wave absorption improved with the increase of TiO₂ powder in the mixture. The mixture with micro-sized TiO₂ powder was a little more effective in causing power loss of EM waves than the mixture with nano-sized TiO₂ powder.     

Studies on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> high K gate dielectrics applied in a fully depleted SOI MOSFET

Al₂O₃/ZrO₂/Al₂O₃ gate stacks were prepared on ultrathin SOI (Silicon on insulator) substrates by ultrahigh vacuum electron beam evaporation and post-annealed in N₂ at 450°C for 30 min. Three clear nanolaminate layered structure of Al₂O₃(2.1 nm)/ZrO₂(3.5 nm)/Al₂O₃(2.3 nm) was observed with a high-resolution cross-sectional transmission electron microscope (HR-XTEM). High frequency capacitance voltage (C-V) characteristics of a fully depleted (FD) SOI MOS capacitor at 1 and 5 MHz were studied. The minority carriers determine the high frequency C-V properties, which is opposite to the case of bulk MOS capacitors. The series resistance of the SOI substrate is found to be the determinant factor of the high frequency characteristics of FD SOI MOS capacitors. 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.     

In situ synthesis of Co3O4/graphene nanocomposite material for lithium-ion batteries and supercapacitors with high capacity and supercapacitance

Co₃O₄/graphene nanocomposite material was prepared by an in situ solution-based method under reflux conditions. In this reaction progress, Co²⁺ salts were converted to Co₃O₄ nanoparticles which were simultaneously inserted into the graphene layers, upon the reduction of graphite oxide to graphene. The prepared material consists of uniform Co₃O₄ nanoparticles (15-25 nm), which are well dispersed on the surfaces of graphene nanosheets. This has been confirmed through observations by field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. The prepared composite material exhibits an initial reversible lithium storage capacity of 722 mAh g⁻¹ in lithium-ion cells and a specific supercapacitance of 478 F g⁻¹ in 2 M KOH electrolyte for supercapacitors, which were higher than that of the previously reported pure graphene nanosheets and Co₃O₄ nanoparticles. Co₃O₄/graphene nanocomposite material demonstrated an excellent electrochemical performance as an anode material for reversible lithium storage in lithium ion cells and as an electrode material in supercapacitors.     

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.     

Cold spray of SiC and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with soft metal incorporation: A technical contribution

Al + SiC, Al + Al₂O₃ composites as well as pure Al, SiC, and Al₂O₃ coatings were prepared on Si substrates by the cold gas dynamic spray process (CGDS or cold spray). The powder composition of metal (Al) and ceramic (SiC, Al₂O₃) was varied into 1:1 and 10:1 wt.%, respectively. The propellant gas was air heated up to 330 °C and the gas pressure was fixed at 0.7 MPa. SiC and Al₂O₃ have been successfully sprayed producing coatings with more than 50 μm in thickness with the incorporation of Al as a binder. Also, hard ceramic particles showed peening effects on the coating surfaces. In the case of pure Al metal coating, there was no crater formation on hard Si substrates. However, when Al mixed with SiC and Al₂O₃, craters were observed and their quantities and sizes depended on the composition, aggregation and size of raw materials.     

Thermodynamic optimization of the Na<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript> pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

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.     

Microemulsion synthesis and magnetic properies of BaAl<Subscript>4</Subscript>Fe<Subscript>8</Subscript>O<Subscript>19</Subscript> powders

Al-substituted M-type hexaferrite is a highly anisotropic ferromagnetic material. In the present study, we report the synthesis and the characterization of BaAl₄Fe₈O₁₉ powder from two microemulsion systems of po1yoxyethylene octylphenol ether/1, 2-propylene glycol, or ethanol/cyclohexane/water and cetrimonium bromide/1, 2-propylene glycol/cyclohexane/water. Two microemulsion systems were found to give wide stable regions. The synthesized powders were characterized with x-ray diffraction, scanning electron microscopy, and vibrating sample magnetometer. The experiment results indicated that the surfactant, co-surfactant, and oil/water ratio remarkably affected the particle size, size distribution, anisotropy and magnetic property of the powders. The powder prepared with microemulsion of po1yoxyethylene octylphenol ether/1, 2-propylene glycol/cyclohexane/water exhibited best particle character, that is, uniform thin particle morphology, large shape anisotropy, small particle size, large coercivity of 8.73 kOe, and saturation magnetization of 20.821 emu·g⁻¹.