Papers by Author: Eiichiro Matsubara

Abstract: Rechargeable Mg batteries have received intensive attention as affordable rechargeable batteries with high electromotive force, high energy density, and high safety. Mg possesses two valence electrons and has the lowest standard electrode potential (ca. -2.36 V vs. SHE) among the air-stable metals. There is another advantage that Mg metal can be used as an active material because Mg metal hardly forms dendrites. However, the slow diffusion of Mg ions in solid crystals prevents the realization of active materials for Mg rechargeable batteries at room temperature. Although some complex oxides have been reported to work as active materials at higher temperatures, Chevrel compounds are still the gold standards, which work at room temperature. However, the working voltage of the Mg battery using a Chevrel compound for the cathode is only ca. 1.2 V, which is far below that of Li-ion batteries (3-5 V). Nevertheless, Chevrel compounds have the significant advantage that a relatively large space exists in the crystal structure, which allows for fast Mg ion diffusion. In the present study, we investigated some materials with framework structures as cathodes for Mg batteries, which can alleviate the electrostatic constraint between Mg ions and cathode constituents. Specifically, we investigated the redox behavior of the thin films of Prussian blue and Prussian blue analogues in electrolytes containing an Mg salt using electrochemical quartz crystal microbalance and X-ray absorption spectroscopy. In addition, we discuss the electrochemical insertion/extraction behavior of Mg ions and their solvation structures.

Abstract: The structure, thermal stability and elasticity of Zr50Cu40Al10 bulk metallic glass (BMG) have been investigated with reference to Zr70Cu30 and Zr70Cu20Al10 amorphous alloys. The thermal stability of Zr50Cu40Al10 is significantly enhanced in comparison compared with those of the others. The large total coordination numbers more than 11 around all constituent elements are observed in Zr50Cu40Al10. A change of the bulk modulus in the crystallization is extremely small in Zr50Cu40Al10. The present experimental results indicate that atoms in the Zr50Cu40Al10 glass are closely packed and its microstructure is fairly uniform. This results in the much higher thermal stability of Zr50Cu40Al10.

Abstract: It has been reported that accumulative-roll-bonded (ARB) aluminum having ultrafine grains shows an intriguing mechanical character that it is hardened by annealing and contrarily softened by deformation. In order to understand the mechanism of such a peculiar phenomenon, we have investigated the dislocation damping with ultrasonic spectroscopy and total amount of dislocations with the X-ray diffraction measurement. From the present measurements, we have found that the dislocations introduced by the ARB process are tangled but can be released with a large stress. Such dislocations accumulated in ultrafine grains play a significant role in the plastic deformation.

Abstract: Temperature dependent elastic constants Cij(T) of Cu60Hf30Ti10 bulk metallic glass (BMG) have been investigated in a MHz frequency range using electromagnetic acoustic resonance (EMAR) up to 823 K. At room temperature, the BMG showed high Poisson’s ratio ν arising from low shear modulus G compared with that of constitutive crystalline elements. With increasing temperature, G showed usual linear temperature dependence while it suddenly drops around glass transition temperature, Tg. Within a framework of quasiharmonic approximation, Grüneisen parameter γ around Tg is estimated to be 10. This extremely large γ indicates the high anhramonicity of long wavelength limit acoustic mode phonon in the supercooled liquid state. The unusual elastic behavior can be interpreted on the basis of heterogeneous microstructure.