On a new calcium vanadate: synthesis, structure and Li insertion behavior

A synthetic form of the mineral hewettite was prepared via a new route in aqueous medium, starting either from the crystalline compound Li_1.1V₃O₈, or from its amorphous precursor. The anhydrous, crystalline derivative Ca_0.5V₃O₈ was obtained by heating the synthetic hewettite at 250°C under dynamic vacuum. The diffraction studies show that the 2D structure of Ca_0.5V₃O₈ involves the same V₃O₈ layers as in the hewettite or in Li_1+αV₃O₈. The stacking of the layers is similar to that in the metahewettite. A structural model is proposed, where the Ca²⁺ ions occupy octahedral sites in the interlayer space. The electrochemical behavior of Ca_0.5V₃O₈ vs. lithium insertion is presented. It is original and reveals particularly good performances in terms of stability during cycling at C/5 rate. The homologues obtained with Mg or Ba, instead of Ca, are briefly presented.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Deposition conditions in tailoring the morphology of highly porous reticular films prepared by electrostatic spray deposition (ESD) technique

Spongy-like reticular structure is a unique morphology fabricated by electrostatic spray deposition (ESD) technique. The effects of solvent, substrate temperature, precursor feeding rate, static electric field strength, and deposition time on tailoring the reticular structure were investigated. Scanning electron microscopy was used to observe the film morphology. MnO_x or LiMn₂O₄ were selected as the model materials. It is found that in addition to the conventional solvent butyl carbitol, other kinds of solvents such as ethylene glycol and propylene glycol can also be used to obtain reticular films at a suitable substrate temperature. Porous films with a low cross-linking degree pore structure can be prepared by increasing precursor feeding rate or decreasing substrate temperature. Increasing the deposition time or the electric field strength helps to obtain reticular films with more homogeneous pore size distribution. In addition, the addition of a high boiling-point solvent in mixed alcohol solvent results in the increase of proper substrate temperature. It is concluded that the fluidity of the spray droplets on the surface of a hot substrate is an important factor to form a reticular film.     

Low sintering temperature MnZn-ferrites for power applications in the frequency region of 400 kHz

In this paper, the effect of cubic zinc metaborate Zn₄O(BO₂)₆ on the sintering of MnZn-ferrites for medium frequency power applications is investigated. Zinc metaborate is synthesized in the laboratory using zinc oxide and boric acid as metal precursors. As observed, when zinc metaborate is added to the MnZn-ferrites at an optimum amount of 0.02 wt%, it significantly enhances densification and therefore allows, for a given density, reduction of the firing temperature by almost 200 °C. MnZn-ferrites exhibiting power losses of 70 mW/cm³ (measured at a frequency of 400 kHz, magnetic field 50 mT and temperature of 90 °C) are synthesized from conventionally milled powders with average particle diameter 0.6 μm, compacted and fired at 1100 °C. Identical experiments conducted under the same conditions on specimens without zinc metaborate additions revealed power losses greater than 300 mW/cm³, because of insufficient densification.     

Hydrothermal synthesis of FeS2 for lithium batteries

Nanocrystalline FeS₂ cathode material of lithium cell was synthesized from cheap materials of FeSO₄, Na₂S₂O₃, and sulfur by a hydrothermal process. The scanning electron microscopy analysis showed the obtained material was nano-sized, about 500 nm. The X-ray powder diffraction analysis showed that the synthetic FeS₂ material had two phases of the crystalline structure, pyrite and marcasite. The phase of marcasite seems to have no negative effect on the electrochemical performance of the material. The synthetic FeS₂ showed a significant improvement of electrochemical performance for Li/FeS₂ cells.     

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.     

Microscopically structural studies of lithium niobate powders

On the basis of the crystallographic characteristics of lithium niobate (LN) crystals, Law of Bravais and Pauling's third rule (i.e. Polyhedral Sharing Rule) are employed with the aim to find the relationship between the crystal structure and morphological faces of LN powders. In order to validate our analytical results, we have successfully synthesized LN powders and measured the corresponding X-ray powder diffraction. Our results show that the structural analysis is consistent with the experimental data and is helpful and effective for us to control the single-crystal growth and to design superstructures at the specific plane, starting from the viewpoint of the microscopic behaviors of constituent chemical bonds and polyhedra in the crystallographic frame.