Analysis of cationic structure in some room-temperature molten fluorides and dependence of their ionic conductivity and viscosity on hydrofluoric acid concentration.

To understand the ionic and nonionic species in (CH(3))(4)NF·mHF, (CH(3))(3)N·mHF, (C(2)H(5))(4)NF·mHF, and (C(2)H(5))(3)N·mHF melts, the structures of these melts were investigated by infrared spectroscopy, NMR, and high-energy X-ray diffraction. Infrared spectra revealed that three kinds of fluorohydrogenate anions, (FH)(n)F(-) (n = 1, 2, and 3), and molecular hydrofluoric acid (HF) are present in every melt. Ionic conductivity and viscosity of these melts were measured and correlated with their cationic structure. The ionic conductivity of the R(4)N(+)-systems was higher than that of corresponding R(3)NH(+)-systems because a strong N-H···F(HF)(n) interaction prevents the motion of R(3)NH(+) cations in the R(3)N·mHF melts. (CH(3))(4)N(+) and (CH(3))(3)NH(+) cations gave higher ionic conductivity than (C(2)H(5))(4)N(+) and (C(2)H(5))(3)NH(+) cations, respectively, because the ionic radii of former cations were smaller than those of latter. It was concluded that these effects on ionic conductivity can be explained by the cationic structure and the concentration of molecular HF in the melts.

Preparation of core/shell and hollow nanostructures of cerium oxide by electrodeposition on a polystyrene sphere template.

Core/shell nanostructures of polystyrene (PS)/CeO2 have been prepared on conductive glass substrates by using a novel electrochemical route consisting of (i) the electrophoretic deposition of a PS sphere monolayer on the substrate and (ii) the following potentiostatic electrodeposition of CeO2 on the PS sphere template in Ce(NO3)3 aqueous solutions. The structural morphologies of the deposit changed drastically depending on the Ce(NO3)3 concentration; i.e., spherical and needlelike shells were deposited. The deposit was formed only on the PS sphere surface because of an interaction between cationic cerium species and a sulfate group that was immobilized on the PS sphere surface. The spherical shell layer was assigned as CeO2, and the needlelike shells were composed of Ce(OH)3 needles formed on the CeO2 layer surface, indicating that the deposit species changes from CeO2 to Ce(OH)3 during electrodeposition only in a 1 mM Ce3+ solution. Deposition of Ce(OH)3 would begin when electrogenerated hydrogen peroxide was consumed by decomposition under reductive conditions and could no longer oxidize Ce3+ ions. The corresponding CeO2 hollow shells were obtained by thermal elimination of the PS sphere core and transformation of Ce(OH)3 into CeO2 while keeping their original shapes.

Atomic force microscopy study on the stability of a surface film formed on a graphite negative electrode at elevated temperatures.

The stability at elevated temperatures of a solid electrolyte interphase (SEI) formed on a graphite negative electrode in lithium ion batteries was investigated by storage tests and in situ atomic force microscopy (AFM) observation. When the fully discharged graphite electrode was stored at elevated temperatures, the irreversible capacity in the following cycle increased remarkably. On the other hand, when the electrode was stored at the fully charged state at elevated temperatures, it was severely self-discharged during storage. AFM observation of the SEI layer formed on a model electrode of highly oriented pyrolytic graphite revealed two important facts on the stability of the SEI at elevated temperatures: (i) dissolution and agglomeration of the SEI layer at the discharged state and (ii) serious SEI growth at the charged state. These phenomena well explain the results of the charge and discharge tests. It was also shown that the addition of vinylene carbonate greatly improves the stability of the SEI at elevated temperatures, and gives good charge and discharge performance after storage.