Lithiation of InSb and Cu2_2Sb : A Theoretical Investigation

In this work the mechanism of Li insertion/intercalation in the anode materials InSb and Cu$_2$Sb is investigated by means of the first principles total energy calculations. The total charge densities for the lithiated products of the two compounds are presented. Based on these results the change in the bonding character on lithiation is discussed. Further, the isomer shift for InSb and Cu$_2$Sb and there various lithiated products is reported. The average insertion/intercalation voltage and volume expansion for transitions from InSb to Li$_2$InSb and Cu$_2$Sb to Li$_2$CuSb are calculated and found to be in good agreement with the experimental values. These findings help to resolve the controversy regarding the lithiation mechanism in InSb.Comment: 5 pages 3 figure

On the effect of heterovalent substitutions in ruthenocuprates

We discuss the properties of superconducting derivatives of the RuSr2GdCu2O8 (1212-type) ruthenocuprate, for which heterovalent doping has been achieved through partial substitution of Cu ions into the RuO2 planes (Ru1-xSr2GdCu2+xO8-d, 0<x<0.75, Tcmax=72 K for x=0.3-0.4) and Ce ions into the Gd sites (RuSr2Gd1-yCeyCu2O8, 0<y<0.1). The measurements of XANES, thermopower, and magnetization under external pressure reveal an underdoped character of all compounds. Muon spin rotation experiments indicate the presence of magnetic order at low temperatures (Tm=14-2 K for x=0.1-0.4). Properties of these two series lead us to the qualitative phase diagram for differently doped 1212-type ruthenocuprates. The difference in temperature of magnetic ordering found for superconducting and non-superconducting RuSr2GdCu2O8 is discussed in the context of the properties of substituted compounds. The high pressure oxygen conditions required for synthesis of Ru1-xSr2RECu2+xO8-d, have been extended to synthesis of a Ru1-xSr2Eu2-yCeyCu2+xO10-d series. The Cu->Ru doping achieved in these phases is found to decrease the temperature for magnetic ordering as well the volume fraction of the magnetic phase.Comment: Proceedings of the 3rd Polish-US Workshop on Magnetism and Superconductivity of Advanced Materials, July 14-19, 2002, Ladek Zdroj (Poland) to appear in Physica

Olivine Composite Cathode Materials for Improved Lithium Ion Battery Performance

Composite cathode materials in lithium ion batteries have become the subject of a great amount of research recently as cost and safety issues related to LiCoO2 and other layered structures have been discovered. Alternatives to these layered materials include materials with the spinel and olivine structures, but these present different problems, e.g. spinels have low capacities and cycle poorly at elevated temperatures, and olivines exhibit extremely low intrinsic conductivity. Previous work has shown that composite structures containing spinel and layered materials have shown improved electrochemical properties. These types of composite structures have been studied in order to evaluate their performance and safety characteristics necessary for use in lithium ion batteries in portable electronic devices, particularly hybrid-electric vehicles. In this study, we extended that work to layered-olivine and spinel-olivine composites. These materials were synthesized from precursor salts using three methods: direct reaction, ball-milling, and a coreshell synthesis method. X-ray diffraction spectra and electrochemical cycling data show that the core-shell method was the most successful in forming the desired products. The electrochemical performance of the cells containing the composite cathodes varied dramatically, but the low overpotential and reasonable capacities of the spinel-olivine composites make them a promising class for the next generation of lithium ion battery cathodes

Altering the Equilibrium Condition in Sr-Doped Lanthanum Manganite

The material of choice for a solid oxide fuel cell cathode based on a yttria-stabilized zirconia (YSZ) electrolyte is doped lanthanum manganite, (La, Sr)MnO{sub 3}. It excels at many of the attributes necessary for a system to work at the required operating temperature and is flexible enough to allow for materials optimization. Although strontium-doping increases the electronic conductivity of the material, the ionic conductivity of the material remains negligible under operating conditions. Studies have shown that the internal equilibrium of the material heavily favors oxidation of the manganese and rather than the loss of lattice oxygen as a charge compensation mechanism. This lack of oxygen vacancies in the structure retards the ability of the material to conduct oxygen ions; thus the optimized system requires a large number of engineered triple point boundary locations to work efficiently. We have successfully doped the host LSM lattice to alter the interred equilibrium of the material to increase its ionic conductivity and thus lower the cathodic overpotential of the system. Our presentation will discuss these new materials, the results of cell tests, and a number of characterization experiments performed