X-ray absorption near-edge structure study on positive electrodes of degraded lithium-ion battery

18650-type cylindrical cells using LiNi_1/3Mn_1/3Co_1/3O₂ (NMC) and hard carbon as positive and negative electrode material, respectively, were fabricated and degraded by cycle tests. The capacity of the cells remained more than 95% and 85% after cycle tests at 25 and 50 °C, respectively. After the cycle tests, Li-deficient cubic phase was observed on the surface of NMC. This phenomenon should be related to the degradation mechanism of this type of cell.     

Fe content effects on electrochemical properties of Fe-substituted Li2MnO3 positive electrode material

Fe-substituted Li₂MnO₃ including a monoclinic layered rock-salt structure (C2/m), (Li_1+x(Fe_yMn_1−y)_1−xO₂, 0 < x < 1/3, 0.1 ≤ y ≤ 0.5) was prepared by coprecipitation-hydrothermal-calcination method. The sample was assigned as two-phase composite structure consisting of the cubic rock-salt () and monoclinic ones at high Fe content above 30% (y ≥ 0.3), while the sample was assigned as a monoclinic phase (C2/m) at low Fe content less than 20%. In the monoclinic Li₂MnO₃-type structure, the Fe ion tends to substitute a Li (2b) site, which corresponds to a center position of Mn⁴⁺ hexagonal network in Mn-Li layer. The electrochemical properties including discharge characteristics under high current density (<3600 mA g⁻¹ at 30 °C) and low temperature (<−20 °C at 40 mA g⁻¹) were severely affected by chemical composition (Fe content and Li/(Fe + Mn) ratio), crystal structure (monoclinic phase content) and powder property (specific surface area). Under the optimized Fe content (0.2 < y < 0.4), the Li/sample cells showed high initial discharge capacity (240-300 mAh g⁻¹) and energy density (700-950 mWh g⁻¹) between 1.5 and 4.8 V under moderate current density, 40 mA g⁻¹ at 30 °C. Results suggest that Fe-substituted Li₂MnO₃ would be a non-excludable 3 V positive electrode material.     

Electrophoretic cell manipulation and electrochemical gene-function analysis based on a yeast two-hybrid system in a microfluidic device

A novel microfluidic device with an array of analytical chambers was developed in order to perform single-cell-based gene-function analysis. A series of analytical processes was carried out using the device, including electrophoretic manipulation of single cells and electrochemical measurement of gene function. A poly(dimethylsiloxane) microstructure with a microfluidic channel (150 microm in width, 10 microm in height) and an analytical chamber (100 x 20 x 10 microm (3)) were fabricated and aligned on a glass substrate with an array of Au microelectrodes. Two microelectrodes positioned in the analytical chamber were employed as a working electrode for the electrophoretic manipulation of cells and electrochemical measurements. A yeast strain ( Saccharomyces cerevisiae Y190) carrying the beta-galactosidase reporter gene was used to demonstrate that the device could detect the enzyme. Target cells flowing through the main channel were introduced into the chamber by electrophoresis using the ground electrode laid on the main channel. When the cell was treated with 17beta-estradiol, gene expression was triggered to produce beta-galactosidase, catalyzing the hydrolysis of p-aminophenyl-beta- D-galactopyranoside to form p-aminophenol (PAP). The enzymatically generated PAP was detected by cyclic voltammetry and amperometry at the single-cell level in the chamber of the device. Generator-collector mode amperometry was also applied to amplify the current response originating from gene expression in the trapped single cells. After electrochemical measurement, the trapped cells were easily released from the chamber using electrophoretic force.     

A method for dispersing dry nano-sized particles in a liquid using carrier particles

A method for dispersing dry particles in a liquid is described. The method involves coating large carrier particles with fine particles. When two types of particles having different sizes are mixed in dry conditions, the particles adhere to one another, and the large particles become coated with small particles. When the large core particles are coated with a mono-layer of small particles, further agglomeration is inhibited. Because the single small particles generated by the disruption adhere to the core particles, we presumed that, if the small particles that are adhered to large particles could be separated from the large particles by a sonication in a liquid, the dry fine particles could be dispersed in a liquid.The dispersion experiments conducted using spherical silica particles having a count median diameter D_p50 of 74 nm as small particles and spherical glass beads as large particles. In this situation, the large particles carry the small particles from a dry condition into a liquid. We refer to the large particles as carrier particles. The experiments revealed that the proposed dispersion procedure results in a superior product, compared to sonication only. The effect of carrier size on dispersion performance is also investigated. The findings indicate and an optimum carrier size exists. Observations of the carrier particle surfaces after dry mixing indicate that the optimum condition is the condition at which a mono-layer of Silica particles is formed.     

Influence of Diffused Boron Into MgO Barrier on Pinhole Creation in CoFeB/MgO/CoFeB Magnetic Tunnel Junctions

A relationship between boron (B) diffusion into the MgO barrier and pinhole creation in CoFeB/MgO/CoFeB-magnetic tunnel junctions (MTJs) was investigated. The diffused B in the MgO layer was identified by secondary ion mass spectrometry for the MTJs annealed at 350degC , which provide the giant magnetoresistance (TMR) ratio. The pinhole density, estimated from the statistic distribution of breakdown voltage of the TMR properties, increased as either the thickness or the B content of the CoFeB layer became thicker or higher. These experimental findings imply that the diffused B into the MgO barrier creates pinholes to short-circuit the tunnel conduction, since the amount of diffused B into the MgO barrier might be related to the total amount of the B content in the CoFeB layer. Three different techniques were found to be useful for the reduction of diffused B into the MgO barrier layer; usage of materials having boron affinity for capping layer, decrease of the total amount of B-content in CoFeB layer, and reduction of grain boundaries in the MgO barrier layer.     

Immunolocalization of multiple membrane proteins on a carbon replica with STEM and EDX

We present a method for immunolabeling of multiple species of membrane proteins with high spatial resolution. It allows differentiation of equally sized very small markers with different chemical compositions, which leads to high labeling efficiency and reduces steric hindrance of closely spaced immunolabeled biomolecules. Markers such as CdSe/ZnS semiconductor quantum dots and colloidal gold particles are distinguished by differential contrast in high-angle annular detector dark-field STEM mode or by EDX microanalysis of their elemental contents. This method was tested by observation of labeled AMPA- and NMDA-type glutamate receptors on sodium-dodecyl-sulfate-digested replica prepared from rat hippocampus. To improve particle visibility and detectability, the replica films were made exclusively with carbon to avoid the high background of conventional platinum/carbon replica. Extension of the method is suggested by detection of 1.4 nm nanogold particles and its potential application in the biological imaging research.     

Photovoltaic effect based on wet poly(vinyl alcohol)/merocyanine dye junction

The sandwich cell, Au/wet poly(vinyl alcohol) (PVA)/merocyanine (MD)/Au, based on the PVA/MD junction exhibited photovoltaic and rectifying effects. Forward dark current from the MD/Au electrode to the counter PVA/Au electrode through the cell was observed. The Au/MD electrode showed a positive photovoltage with respect to the PVA/Au electrode regardless of the direction of the incident light. It was suggested that a heterojunction barrier similar to the Schottky type formed at polymer/dye interface was responsible for the photo charge separation.