Chihiro Yogi

Promoting formation of noncrystalline Li2O2 in the Li-O2 battery with RuO2 nanoparticles.

Low electrical efficiency for the lithium-oxygen (Li-O2) electrochemical reaction is one of the most significant challenges in current nonaqueous Li-O2 batteries. Here we present ruthenium oxide nanoparticles (RuO2 NPs) dispersed on multiwalled carbon nanotubes (CNTs) as a cathode, which dramatically increase the electrical efficiency up to 73%. We demonstrate that the RuO2 NPs contribute to the formation of poorly crystalline lithium peroxide (Li2O2) that is coated over the CNT with large contact area during oxygen reduction reaction (ORR). This unique Li2O2 structure can be smoothly decomposed at low potential upon oxygen evolution reaction (OER) by avoiding the energy loss associated with the decomposition of the more typical Li2O2 structure with a large size, small CNT contact area, and insulating crystals.

Photocatalytic degradation of methylene blue by Au-deposited TiO2 film under UV irradiation

A TiO2 photocatalytic film was prepared by the sol–gel and dip-coating methods. Au-loaded TiO2 photocatalytic films were produced by the photodeposition method. The photocatalytic activity of the films under UV irradiation was evaluated by measuring the degradation of absorbance for a methylene blue (MB) aqueous solution. Au particles deposited on the TiO2 film improved the photocatalytic activity under the O2 bubbling condition. On the other hand, under N2 or Ar bubbling, the doubly reduced form of MB, leuco-methylene blue (LMB), was formed at the beginning of UV irradiation, and then both MB and LMB were decomposed gradually by the photocatalytic reaction. In this process, Au particles on the TiO2 film behave as electron traps.

A structured three-dimensional polymer electrolyte with enlarged active reaction zone for Li-O2 batteries

The application of conventional solid polymer electrolyte (SPE) to lithium-oxygen (Li–O2) batteries has suffered from a limited active reaction zone due to thick SPE and subsequent lack of O2 gas diffusion route in the positive electrode. Here we present a new design for a three-dimensional (3-D) SPE structure, incorporating a carbon nanotube (CNT) electrode, adapted for a gas-based energy storage system. The void spaces in the porous CNT/SPE film allow an increased depth of diffusion of O2 gas, providing an enlarged active reaction zone where Li+ ions, O2 gas, and electrons can interact. Furthermore, the thin SPE layer along the CNT, forming the core/shell nanostructure, aids in the smooth electron transfer when O2 gas approaches the CNT surface. Therefore, the 3-D CNT/SPE electrode structure enhances the capacity in the SPE-based Li–O2 cell. However, intrinsic instability of poly(ethylene oxide) (PEO) of the SPE matrix to superoxide (O2·−) and high voltage gives rise to severe side reactions, convincing us of the need for development of a more stable electrolyte for use in this CNT/SPE design.

Atomic-scale disproportionation in amorphous silicon monoxide

Solid silicon monoxide is an amorphous material which has been commercialized for many functional applications. However, the amorphous structure of silicon monoxide is a long-standing question because of the uncommon valence state of silicon in the oxide. It has been deduced that amorphous silicon monoxide undergoes an unusual disproportionation by forming silicon- and silicon-dioxide-like regions. Nevertheless, the direct experimental observation is still missing. Here we report the amorphous structure characterized by angstrom-beam electron diffraction, supplemented by synchrotron X-ray scattering and computer simulations. In addition to the theoretically predicted amorphous silicon and silicon-dioxide clusters, suboxide-type tetrahedral coordinates are detected by angstrom-beam electron diffraction at silicon/silicon-dioxide interfaces, which provides compelling experimental evidence on the atomic-scale disproportionation of amorphous silicon monoxide. Eventually we develop a heterostructure model of the disproportionated silicon monoxide which well explains the distinctive structure and properties of the amorphous material.

A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K- and L-edge XANES spectral simulations and resonance photoelectron spectroscopy

X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for disti...

Photocatalytic Properties of Size-Controlled Titania Nanotube Arrays

The titania nanotube arrays (TNAs) with smooth surface was synthesized by anodization of titanium foil with 3 cm2 in square area using the electrolyte composed of 0.2 wt% NH4F and 0.5 vol% H2SO4 in ethylene glycol in order to evaluate the methylene blue photodegradation under ultra-violet irradiation. The tube length and inner diameter as a size parameter were controlled by the anodization time from 5 to 10 h and applied voltage from 10 to 50 V. The titania nanotube arrays (TNAs) annealed at 300 to 500°C were assigned to anatase phase, and TNAs at 600°C had both phase of anatase and rutile. The crystallite size and the apparent rate constant were increased with the increase in the annealing temperature of TNAs from 300 to 500°C. The bigger crystallite size of TNAs is suggested to be related to the increase in the amount of hole at the valence band, leading to the decrease in the apparent rate constant of MB degradation. Interestingly, the four kinds of linear relationship with the apparent rate constant were seen in both the inner diameter of TNAs and the length. Consequently, the apparent rate constant strongly depended on inner diameter of TNAs.

Self-Organization of Gold Nanoparticles Coated with a Monolayer of Azobenzene Liquid Crystals

A gold nanoparticle having a monolayer of azobenzene liquid crystal (LC) was synthesized. The size of the gold nanoparticle obtained was 4.7 nm in average diameter, and it was soluble in common non-polar organic solvents such as toluene and dichloromethane. We confirmed that the reversible photochemical and thermal isomerization of the azobenzene could take place on the surface of the gold nanoparticles in analogy with free azobenzenes in solutions. Furthermore, a 1-dimensional self-organization of the nanoparticle was observed by transmission electron microscopy. However, a gold nanoparticle without LC molecules never showed such self-organization. Therefore, we conclude that the self-organization of the gold nanoparticle is based on the liquid crystallinity of the organic ligands attached on their surface.