Technology of electrochemical impedance spectroscopy for an energy-sustainable society

Electrochemical impedance spectroscopy has been widely used to understand the chemistry and physics of battery systems. This review covers electrochemical impedance spectroscopy used for the interpretation of impedance data of lithium-ion batteries (LIBs) from advanced equivalent circuit models to the mathematical model, which is developed by John Newman. In addition, as a method to realize an energy-sustainable society using diagnostics based on the combination of LIBs and electrochemical impedance spectroscopy, on-board diagnostics of battery packs are achieved based on an input signal generated by a power controller in a battery management system instead of the conventionally used frequency response analyzer. The diagnostic system is applicable to energy management systems which are installed in homes, buildings, and communities, accumulating the impedance data on state of health of LIBs. Finally, a future possibility regarding the diagnostics of battery packs coupled with the machine learning of impedance data is introduced.     

Electroluminescence properties of electropolymerized poly (para-phenylene) films by means of electrochemical oxidation and reduction

We investigated electroluminescence (EL) properties of electropolymerized poly-p-phenylene (PPP) films formed by means of electro-oxidative and electro-reductive methods. Electro-oxidatively polymerized PPP (O-PPP) and electro-reductively polymerized PPP (R-PPP) clearly demonstrated different light emitting behavior. In the case of electro-oxidative PPP, the intensity of light emission decreased with increasing quantity of polymerization charge, whereas with electro-reductive PPP, it increased with increasing quantity of polymerization charge. These different types of behavior of the two kinds of PPP films suggested the difference in depth profile of the regularity of molecular structures formed by the two different methods.     

Enantioselective syntheses of the assigned structures of the helibisabonols A and B

The enantioselective syntheses of the compounds with the assigned structures of the helibisabonols A and B have been accomplished. Using an enzymatic desymmetrization of the σ-symmetrical diol (route a) and a diastereoselective conjugate addition of the methyl to the enone with a chiral auxiliary (route b) we constructed the key tertiary stereogenic center at the benzylic position (C7) and then used an asymmetric dihydroxylation for assembling the C10 stereogenic center. In addition, possible diastereoisomers of the natural products were prepared and detailed comparisons of the ¹H and ¹³C NMR spectra were conducted. As a result, the structure originally assigned to helibisabonol A may be revised to (7R,10R)-1. In the case of helibisabonol B, the (7R,10R)-2 would be reasonable based on a comparison of the NMR data and the biogenetic parallelism with helibisabonol A.     

Biaxial Orientation Mechanism of Drawn Natural Rubber. II. Quantitative Analysis of the Biaxial Orientation

Natural rubber film was prepared from triple centrifuged latex. The film was uniaxially drawn at room temperature and the induced crystalline orientation was quantitatively studied by wide angle X‐ray diffraction. The intensity distribution of 200 and 120 reflections confirmed that the induced crystals have a biaxial orientation with the c‐axis parallel to the draw direction. The orientation of the a‐axis was evaluated by using an orientation function of the (200) plane. The function (F ₂₀₀) indicated that the crystalline a‐axis is parallel to the film surface depending on the draw ratio and on positions in the film. The experimental results are possible to explain by shish‐kebab‐like crystallization developed from a highly oriented fibril. The secondary crystallization grows perpendicularly to the draw direction along the a‐axis. The population of the secondary crystals is controlled by an ellipsoidal free space. The shape of the ellipsoid is changed by the fibril distribution depending on width and thickness of the sample film. In this study, the quantitative biaxial orientation is consistently explained by the shish‐kebab‐like crystallization and the ellipsoidal free space.     

In-situ imaging of Li-ion migration at interfaces in an all solid Li-ion battery

We investigated the migration of Li ions at an interface between a Li_xTi₅O₁₂ (LTO) and a solid electrolyte in an all-solid Li-ion battery. The optical reflection of LTO changes with variations in the Li content because the band structures of LTO vary with the changes in the Li content. This enables us to observe Li-ion migration in the interface between the LTO and the solid electrolyte using an optical microscope. To observe the LTO particles optically, they were coated on an indium tin oxide on a glass substrate. Variations in Li migration caused by charging/discharging were clearly observed through the changes in the reflection of the LTO. LTO changed between an insulator Li₄Ti₅O₁₂ of the spinel structure and a conductor Li₇Ti₅O₁₂ of the rock-salt structure according to the changes in the Li content. The spinel LTO has a bandgap energy of approximately 2 eV. When electron–hole pairs were generated, electric strains were produced. Surface force microscopy detected the strains and imaged the distribution of lithiation/delithiation of LTO. Interfacial conduction between a sputtered LTO and Li₃PO₄ particles was imaged with high spatial resolution.     

Reverse current reduction of Ge photodiodes on Si without post-growth annealing Invited Paper

A new approach to reduce the reverse current of Ge pin photodiodes on Si is presented, in which an i-Si layer is inserted between Ge and top Si layers to reduce the electric field in the Ge layer. Without post- growth annealing, the reverse current density is reduced to ～10 mA/cm2 at -1 V, i.e., over one order of magnitude lower than that of the reference photodiode without i-Si layer. However, the responsivity of the photodiodes is not severely compromised. This lowered-reverse-current is explained by band-pinning at the i-Si/i-Ge interface. Barrier lowering mechanism induced by E-field is also discussed. The presented "non-thermal" approach to reduce reverse current should accelerate electronics-photonics convergence by using Ge on the Si complementary metal oxide semiconductor (CMOS) platform.     

Improvement of magnetic properties and read/write characteristics in SmCo5 perpendicular thin films

An SmCo₅ alloy is a promising candidate for ultra-high density magnetic recording media because of its strong uniaxial magnetocrystalline anisotropy, whose constant, K_u, is more than 1.1×10⁸ erg/cm³. Recently, we successfully obtained high perpendicular magnetic anisotropy for a sputter-deposited SmCo₅ thin film by introducing a Cu/Ti dual underlayer. However, it is necessary to improve magnetic properties and read/write (R/W) characteristics for applying SmCo₅ thin films to perpendicular magnetic recording media. In this study, we focused on reduction of magnetic domain size and change of a magnetization reversal process of SmCo₅ perpendicular magnetic thin films by introducing carbon (C) atoms into the constituent Cu underlayer. The magnetic domain size became small and the ratio of coercivity (H_c) against magnetic anisotropy (H_k) which is an index of the magnetization reversal process was increased by adding C atoms. We also evaluated the R/W characteristics of SmCo₅ double-layered media including C atoms. The medium noise was decreased and signal-to-noise ratio increased by introducing the C. The addition of C into the Cu underlayer is effective for changing the magnetization reversal process, reducing medium noise and increasing SNR.     

Substituent effects on the structures of silver complexes with monoazatrithia-12-crown-4 ethers bearing substituted aromatic rings

New 4'-methoxybenzyl-, 4'-methylbenzyl-, benzyl-, 3',5'-difluorobenzyl-, 3',5'-dichlorobenzyl-, and 4'-nitrobenzyl-armed monoazatrithia-12-crown-4 ethers were prepared by the reductive amination of monoazatrithia-12-crown-4 with the appropriate benzenecarbaldehyde in the presence of NaBH(OAc)3. Cold electrospray ionization mass spectrometry and X-ray crystallography show that silver complexes with armed monoazatrithia-12-crown-4 ethers bearing aromatic side arms with electron-donating groups or electron-withdrawing groups are coordination polymers and trimers, respectively. The structures of the silver complexes were strongly dependent on the strength of the CH...pi interactions, which are controlled by substituent effects on the aromatic side arms.     

High field effects in amorphous germanium

Measurements of high field current have been made on amorphous Ge (a-Ge) films over the temperature range from 100 to 300 K. Non-ohmic conduction in a-Ge occurs at electric fields greater than 1–2 × 10⁴ V/cm. Field dependence of the conductivity has been explained in terms of the enhanced emission probability of carriers from the screened coulombic trap centers. Assuming the optical dielectric constant for a-Ge films, the screening length of the trap centers and the density of states at the Fermi level are estimated to be 12 Å and ～6.1 × 10²⁰ cm^?3 eV^?1, respectively.