Effect of solvents on the electrochemistry of olefins and aromatic molecules

Cyclic voltammetry and electrolysis studies were carried out in dimethyl sulfoxide, diglyme and liquid ammonia. The depolarizers were diethyl fumarate, ethyl cinnamate, stilbene and anthracene. The reduction reactions were carried out in the presence of organic halides, phenol, acids and water. The rates of the reactions were measured. The main solvent effect was noticed with water which reacts 100 times faster in diglyme than in liquid ammonia or DMSO. The results of electrolytic experiments with two reactants simultaneously were compared with those predicted from the kinetic data.     

Comparison between potentiostatic and galvanostatic intermittent titration techniques for determination of chemical diffusion coefficients in ion-insertion electrodes

Using well-cycled, thin composite graphite electrodes we analyze carefully the limitations of potentiostatic and galvanostatic intermittent titration techniques (PITT and GITT, respectively) for determination of the differential (incremental) intercalation capacitance, C_dif, and the chemical diffusion coefficient, D, of Li ions in these ion-insertion electrodes (IIEs). We demonstrate the superiority of the GITT over PITT to determine these quantities as the former technique allows for a more accurate determination of C_dif and hence D which closely approach to the spinodal domain related to the first-order phase transition during ion-insertion. We show that GITT is also more effective in eliminating the parasitic contributions of background currents to the total measured response. A pronounced difference in the initial, intrinsic kinetics of formation of a new phase in the bulk of the old one has been observed depending on the direction of titration (phases less saturated with Li are formed faster during deintercalation than the Li-rich phases in the course of intercalation).     

Multiple scattering theory. II. Collision induced dissociation in first order

Computationally tractable formulae for one particle differential cross sections and for coincidence cross sections for atom— diatom collision induced dissociation (CID) are obtained within the framework of first order multiple scattering theory. The first order formulation is then used to analyze the simple “knockout circle” model for CID and to derive a more reliable multiple scattering spectator model. Finally, differential and coincidence cross sections are computed for Li⁺ + H₂ at 2O eV and are compared with experiment. The qualitative insight afforded by coincidence studies of CID is clearly demonstrated.     

The crystal structure of the inorganic surface films formed on Mg and Li intercalation compounds and the electrode performance

A crystallographic approach was applied to elucidate the influence of the nature of the surface films on the electrochemical behavior of Li and Mg intercalation compounds. This paper presents two examples: (1) protection of graphite electrodes by Li₂CO₃ surface films, and (2) the unique electrochemical behavior of Mg-containing Chevrel phases (MgCP) obtained by different synthetic routes. In the former case, the elucidation of the protection mechanism and the explanation of the high performance of such protected electrodes are based on the analysis of possible Li-ion motion in the carbonate crystal structure. In the latter case, a combination of synthesis, electrochemistry and XRD analysis was used to explain an unusual phenomenon: the difference between the excellent electrochemical behavior of the Chevrel phase (CP) based on Cu-leached Cu₂Mo₆S₈ (CuCP), and the poor electrochemical activity of the high-temperature synthesized MgCP, with the same phase composition. It is shown that this phenomenon is caused by MgO formation on the surface of the latter material. The different surface chemistry of the MgCPs obtained by the two different synthetic routes was substantiated by revealing the correlation between the electrochemical activity and the chemical stability of these materials under ambient atmosphere conditions. Dedicated to Prof. Mikhail A. Vorotyntsev on the occasion of his 60th birthday.     

Molten salt synthesis (MSS) of Cu2Mo6S8—New way for large-scale production of Chevrel phases

The Chevrel phase (CP), Mo₆S₈, was found to be an excellent cathode material for rechargeable magnesium batteries. Mo₆S₈ is obtained by a leaching process of Cu₂Mo₆S₈, which removes the copper. A new method of Cu₂Mo₆S₈ production was developed. In contrast to the well-known solid-state synthesis of CP, the method is based on the reaction in a molten salt media (KCl). A fast kinetics of this reaction allows using less active, but more convenient precursors (sulfides instead of sulfur), decreasing temperature and synthesis duration, as well as operation in the inert atmosphere instead of dynamic evacuated systems. It was shown that the composition and the electrochemical behavior of the products obtained by MSS and by the solid-state synthesis are identical. Thus, the molten salt method is extremely attractive for the large-scale production of the active materials for Mg batteries.     

The O(N) vector model in the large-N limit revisited: multicritical points and double scaling limit

The multicritical points of the O(N)-invariant N vector model in the large-N limit are re-examined. Of particular interest are the subtleties involved in the stability of the phase structure at critical dimensions. In the limit N → ∞ while the coupling g → g_c in a correlated manner (the double scaling limit) a massless bound state O(N) singlet is formed and powers of 1/N are compensated by IR singularities. The persistence of the N → ∞ results beyond the leading order is then studied with particular interest in the possible existence of a phase with propagating small mass vector fields and a massless singlet bound state. We point out that under certain conditions the double scaled theory of the singlet field is non-interacting in critical dimensions.     

Selective mono-N-alkylation of 3-amino alcohols via chelation to 9-BBN

[reaction: see text] A method for selective mono-N-alkylation of amino alcohols is introduced. This method relies on formation of a stable chelate with 9-BBN, which serves in the dual roles of protecting and activating the amine group. Three prototypical amino alcohols featuring various three-carbon bridging units led selectively to the monoalkylated derivatives in very high yields. The straightforward synthesis of the N-CD3 derivatives demonstrates the effectiveness of this approach.