Effect of nickel coating on electrochemical performance of graphite anodes for lithium ion batteries

Among the different materials often studied and proposed as negative electrodes for lithium-ion batteries, graphite anodes are the most used in commercial batteries. For this study, synthetic graphite was tested. During the first discharge 0.2 Li ions were consumed for the formation of the SEI film and the capacity reaches about 387 mAh/g. But at the end of the first charge only 72% of the initial charge was recovered (the reversible capacity is about 279 mAh/g). In order to improve this performance we have deposited metallic nickel on graphite with the intention to obtain a homogeneous thin layer able to modify the nature of the SEI film, to allow the diffusion of lithium ions through the protective layer, and also to increase the performance of graphite electrodes. The results show a decrease of the irreversible capacity loss (16% instead of 28% for pure graphite electrodes) as well as better cycleability for a nickel-deposited graphite electrode with only 11% weight ratio of nickel. On the other hand, an increase of the nickel content decreases this performance.     

The role of emitter quasi-bound state and scattering on intrinsic bistability in resonant tunneling diodes

Usually, numerical self-consistent calculations predict a much larger intrinsic bistability region than actually is measured in resonant tunneling diodes (RTDs). In addition, numerical calculations have shown that scattering in the well reduces bistability. We used a unified treatment of current flowing from continuum states and emitter quasi-bound states to show numerically and analytically that not only the scattering in the quantum well but also the scattering in the emitter reduces bistability. Moreover, within the Hartree approximation, bistability occurs by tunneling resonantly between emitter quasi-bound state and well quasi-bound state as a pitchfork bifurcation.     

A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Cation transport by a redox-active synthetic ion channel

The synthesis, cation binding and transmembrane conductive properties of a novel group of synthetic ion channels containing a redox-active centre are described. Experiments using a black lipid membrane preparation revealed that these compounds function effectively as ion channels. Subsequent 23Na NMR spectroscopy studies focused on a synthesized ion channel with a ferrocene centre. When incorporated in vesicular bilayers, this channel was demonstrated to support a Na+ flux that was at least six times faster than ion transport by monensin. Since oxidation of the ferrocene moiety completely inhibited the Na+ transport, the redox-active centre provides a potential mechanism for controlling ion flux.     

Neue stellungsisomere reineckesalzähnliche Verbindungen mit Toluidinen

Zusammenfassung Es wurden eine Reihe von Substitutionsreaktionen mit entwässertem K₃[Cr(NCS)₆] und aromatischen Aminen, ohne Verwendung von Lösungsmitteln, durchgeführt. Es wurde beobachtet, da die sehr schwachen Basen mit p_K-Werten 14–16, wie die isomeren Mono- und Dinitro-aniline, die Anthranil- und Sulfanilsäuren, für diese Substitutionsreaktionen ungeeignet sind. Die Alkyl-anilinderivate, wie daso-, m- undp-Toluidin (p_K=10–11) bilden dagegen leicht reineckesalzähnliche Verbindungen: Amin· H[Cr(Toluidin)₂(NCS)₄]. Die Zusammensetzung der neuen Komplexanionen wurde bei einer Reihe von doppelten Umsetzungsreaktionen mit den Chlorhydraten einiger heterocyclischen Aminen festgestellt.Für die Klärung einiger Strukturfragen wurden spektrophotometrische Untersuchungen im UV und IR durchgeführt und die thermische Stabilität bzw. der Mechanismus des Pyrolysenvorganges auf thermogravimetrischem Wege verfolgt.

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Substitution reactions of anhydrous K₃[Cr(NCS)₆] with aromatic amines without applying of solvents were studied.It was observed, that the very weak bases (pK-values 14–16, e.g. isomeric mono- and dinitro-anilines, the anthranilic and sulfanilic acids) are unsuitable for substitution reactions. The alkylaniline derivates e.g.o-, m- andp-toluidine (pK=10–11) form easily reineckesalt analogous compounds: Amin· ·H[Cr(toluidine)₂(NCS)₄]·The formula of the 3 new complex anions: [Cr(toluidine)₂ (NCS)₄]- was established by preparative methods, with a series of double decomposition reactions, using chlorohydrates of some heterocyclic amines for this purpose. From spectroscopical investigations (UV and IR) some structural problems are resolved and discussed.The thermal stability and the mechanism of pyrolysis of these salts was studied by thermogravimetric analysis.

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Mit 8 Abbildungen     

Synthese und Molekülstruktur neuer Ringsysteme aus 1,1,3,3-Tetrachlor-1,3-diphosphapropan

Synthesis and Molecular Structure of new Ring Systems from 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1 reacts in two different ways to form new heterocycles. Partial oxidation of 1 with tetrachloroorthobenzoquinone furnishes the methylene-bridged λ³P, λ⁵P species 3 . Subsequent reactions with di- and triethylamine lead to the condensed ring system 6 with the P?C bonds connected to a central four-membered ring. Compound 6 displays crystallographic inversion symmetry, a short transannular P? P distance and an extremely distorted tetrahedral coordination geometry at the four-membered ring phosphorus atoms. 1 reacts with 7 to give the heterocycle 8 with a central eight-membered ring involving four phosphorus atoms. The eight – membered ring shows a ?bent”? crown conformation, the condensed five – membered rings display envelope conformation.     

Vanadium Doped Sol-Gel TiO2 Coatings

A study of the experimental conditions required to obtain vanadium doped sol-gel TiO2 coatings is presented. Tetraethyl orthotitanate was employed as the TiO2 source and VCl3, VOSO4 · H2O and VOSO4 dissolved H2SO4 where employed as vanadium sources.Dip coating has been used to produce coatings on silicon wafers, spectral carbon electrodes and titanium electrodes. Both supported and unsupported films have been studied by UV-Vis spectra, IR spectroscopy and X-ray diffraction (XRD). The measurements have been made on samples as prepared and treated thermally at temperatures between 100°C and 300°C. The thermal treatment temperatures have been established from DTA/TGA measurements.The vanadium doped sol-gel TiO2 coatings have been tested as sensors for redox potential measurements in electrochemical processes. The influence of both the thickness of films and the nature of substrate has been investigated.     

Photovoltaic and spectral properties of tetraphenyloporphyrin and metallotetraphenyloporphyrin dyes

Spectroscopical properties and photocurrent (or photovoltage) of tetraphenyloporphyrins and metallotetraphenyloporphyrins in nematic liquid crystal have been studied. Photoelectric response has been measured in an electrochemical cell made of the semitransparent semiconducting and golden electrodes with porphyrin dyes embedded in liquid crystal. Fluorescence, time-resolved luminescence in microsecond time scale and photoacoustic spectra have also been measured. The competition between radiative, non-radiative processes and charge transfer is discussed. It has been shown that effectivity of porphyrins for photocurrent generation depends on the presence/absence of central metal in the macrocycle of porphyrin skeleton and the kind of metal. The schematic model of the contributions of the dye molecule and semiconducting electrode in the electron transfer process is shown.     

Kobalt(III)ammin-derivate einiger Reineckesalz-Analoga mit Xylidinen

Zusammenfassung Es wurden 34 neue Komplexsalze durch doppelte Umsetzung aus wäßr.-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)₄(m-xylidin)₂]^–, [Cr(NCS)₄(p-xyl)₂]^– und Hexammin-, Monoacido-pentammin- und Diacido-tetramminkobalt(III)-komplexsalze erhalten. Es wurden in einigen Fällen Unterschiede in physiko-chemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR _f-Werte, bei den stellungsisomeren Salzen vom Typus: Kation · [Cr(NCS)₄(xyl)₂] und auch bei den Koordinationsisomerpaaren: [Co(DH)₂(m-xyl)₂] [Cr(NCS)₄(p-xyl)₂] und [Co(DH)₂(p-xyl)₂] [Cr(NCS)₄(m-xyl)₂] usw. beobachtet.

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Cobalt(III)ammine derivatives of some reineckate analogues with xylidines

34 new complex salts were prepared by double conversion of the reineckate analogues [Cr(NCS)₄(m-xylidine)₂]^–, [Cr(NCS)₄(p-xyl)₂]^–, with the hexammine-, monoacido-pentammine- and diacidotetrammine-complexes of Co(III). In some of the position and coordination isomeres differences of the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR _f-values were observed.