Room-temperature miscibility gap in LixFePO4

The rechargeable lithium-ion cell is an advanced energy-storage system. However, high cost, safety hazards, and chemical instability prohibit its use in large-scale applications. An alternative cathode material, LiFePO(4), solves these problems, but has a kinetic problem involving strong electron/hole localization. One reason for this is believed to be the limited carrier density in the fixed monovalent Fe(3+)PO(4)/LiFe(2+)PO(4) two-phase electrode reaction in LixFePO4. Here, we provide experimental evidence that LixFePO4, at room temperature, can be described as a mixture of the Fe(3+)/Fe(2+) mixed-valent intermediate LialphaFePO4 and Li1-betaFePO4 phases. Using powder neutron diffraction, the site occupancy numbers for lithium in each phase were refined to be alpha=0.05 and 1-beta=0.89. The corresponding solid solution ranges outside the miscibility gap (0相似文献   

Colloidal platinum in hydrogen-rich water exhibits radical-scavenging activity and improves blood fluidity

The 'colloidal platinum' stabilized with polyvinylpyrrolidone (Pt/PVP-colloid) was dispersed in hydrogen-rich water (HW; hydrogen concentration, 0.82 ppm; oxidation-reduction potential, -583 mV) or regular water (RW; <0.01 ppm, +218 mV). And we evaluated the antioxidant activity of Pt/PVP-colloid in HW or RW on 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging and improvement of blood fluidity under 2,2'-azobis (2-amidinopropane) dihydrochloride (AAPH)-induced oxidative stress. When applied with the 0.25-0.5 ppm Pt/PVP-colloid in RW or HW, the level of DPPH radicals decreased to 77.5-59.6% or 16.1-5.6%, in contrast to the level as high as 81.3% for HW alone, respectively, as measured by an electron spin resonance method. The horse blood, which was subjected to AAPH-induced oxidative stress, was incubated for 24 hr with RW or HW, and thereafter required 13.7 sec (100%) or 5.7 sec (42.3%) for passing through the micro-channels in a rheology equipment. When treated with 0.5-1.0 ppm Pt/PVP-colloid in RW or HW, the blood passage time in the micro-channels decreased dose-dependently to 9.7-7.3 sec (71.6-53.8%) or 4.3-1.3 sec (32.8-10.3%), and the rate of micro-channels clogged with erythrocyte aggregates decreased to 23.8-21.0% or 15.8-9.8%, respectively, from 42.8% for no addition of Pt/PVP. By scanning electron microscopy, AAPH-treated erythrocytes lost intact surface morphology on the membrane together with protrusions and without hollows, being indicative of impaired transforming ability, and the rate of erythrocyte agglutination was increased to 46.2%. When treated the horse blood with HW alone significantly decreased the rate of erythrocyte agglutination to 29.6%, whereas 1.0 ppm Pt/PVP-colloid in RW or HW decreased it to 24.1% or 21.1%, respectively. Thus, DPPH-radical-scavenging and erythrocyte-protecting effects of Pt/PVP-colloid in HW were superior to those of Pt/PVP-colloid in RW or Pt/PVP-free HW. The results could be mainly attributed to the enhanced antioxidant activity of Pt/PVP in HW, which may be due to captured-hydrogen on platinum.     

Characterization of Li<Subscript>2</Subscript>S–P<Subscript>2</Subscript>S<Subscript>5</Subscript>–Cu composite electrode for all-solid-state lithium secondary batteries

Electrochemical performance of the Li₂S–P₂S₅–Cu composite materials was examined in all-solid-state lithium secondary batteries. The 80Li₂S·20P₂S₅ (mol.%) solid electrolyte with the addition of Cu was partially used as an active material with lithium source in all-solid-state cells. The initial discharge capacity of 110 mAh g⁻¹ (normalized by the weight of 80Li₂S·20P₂S₅–Cu), which corresponds to 400 mAh g⁻¹ (normalized by the weight of Li₂S), was obtained in the cell using the 80Li₂S·20P₂S₅–Cu composite electrode with the molar ratio of Li₂S/Cu = 48/52. Cycling performance and reaction mechanism of the electrode in the solid-state cell were investigated.     

Effect of Si on the oxidation reaction of α-Ti(0 0 0 1) surface: ab initio molecular dynamics study

Abstract

We present our ab initio molecular dynamics (MD) study of the effect of Si on the oxidation of α-Ti(0?0?0?1) surfaces. We varied the Si concentration in the first layer of the surface from 0 to 25 at.% and the oxygen coverage (θ) on the surface was varied up to 1 monolayer (ML). The MD was performed at 300, 600 and 973 K. For θ = 0.5 ML, oxygen penetration into the slab was not observed after 16 ps of MD at 973 K while for θ > 0.5 ML, oxygen penetration into the Ti slab was observed even at 300 K. From Bader charge analysis, we confirmed the formation of the oxide layer on the surface of the Ti slab. At higher temperatures, the Si atoms diffused from the first layer to the interior of the slab, while the Ti atoms moved from second layer to the first layer. The pair correlation function shows the formation of a disordered Ti-O network during the initial stage of oxidation. Si was found to have a strong influence on the penetration of oxygen in the Ti slab at high temperatures.     

Patterning cultured cells by visible light illumination with photosensitizers

We showed that PC12 cells and 3T3 cells cultured in dishes were killed by illumination with visible white light from a halogen lamp at 7 x 10(4) lx for 5 min in the presence of either 10 microM hematoporphyrin or 2 microM methylene blue as a photosensitizer. This simple technique, based on the photodynamic reaction via generation of reactive oxygen species can be applicable for patterning cultured cells.     

High‐brightness electron sources for a next‐generation light source based on an energy recovery linac

A high‐brightness electron source of ultrasmall emittance and high average current is one of the most important components for next‐generation light sources based on an energy‐recovery linac (ERL). Such a high‐brightness electron source can be realized by a DC photocathode gun driven by laser pulses tailored in the temporal and spatial dimensions. We propose a novel photocathode based on a quantum cascade laser (QCL). Since the ultrafast response of photoelectron emission from QCL is compatible with the tailored laser pulses, it is a candidate electron source for ERLs. © 2011 Wiley Periodicals, Inc. Electr Eng Jpn, 177(3): 46–53, 2011; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.21154     

All-solid-state rechargeable lithium batteries with Li2S as a positive electrode material

The Li₂S–Cu composite electrode materials were prepared by mechanical milling and applied to all-solid-state lithium cells using the Li₂S–P₂S₅ glass–ceramic electrolyte. The addition of Cu and the mechanical activation improved the electrochemical performance of Li₂S in all-solid-state cells. The In/Li₂S–Cu cells were charged and then discharged at room temperature, suggesting that Li₂S was utilized as a lithium source. The cells exhibited high discharge capacity of about 490 mAh g⁻¹ at the 1st cycle. The SEM and EDX analyses suggested that the amorphous Li_xCuS domain was partially formed by milling, and the domain played an important role in the improvement of capacity. The electrochemical reaction mechanism of the Li₂S–Cu composites was discussed on the basis of the mechanism of the S–Cu composite electrode.     

All solid-state battery with sulfur electrode and thio-LISICON electrolyte

A high-capacity type of all solid-state battery was developed using sulfur electrode and the thio-LISICON electrolyte. New nano-composite of sulfur and acetylene black (AB) with an average particle size of 1–10 nm was fabricated by gas-phase mixing and showed a reversible capacity of 900 mAh g⁻¹ at a current density of 0.013 mA cm⁻².     

All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON

All solid-state sheet lithium battery was developed using inorganic solid electrolyte, thio-LISICON (Li_3.25Ge_0.25P_0.75S₄), Li–Al anode, and Mo₆S₈ cathode materials, and the sheet manufacturing process was established. The new sheet-configuration was consisted of the cathode with the grid of current collector, electrolyte sheet with or without mechanical support, and aluminum/lithium composite sheet anode. A sheet battery with a dimension of 30 mm × 30 mm showed good charge–discharge characteristics without any capacity fading at a current of 0.1 mA.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.