Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition.     

Images of locally finite derivations of polynomial algebras in two variables

In this paper we show that the image of any locally finite k-derivation of the polynomial algebra k[x,y] in two variables over a field k of characteristic zero is a Mathieu subspace. We also show that the two-dimensional Jacobian conjecture is equivalent to the statement that the image of every k-derivation D of k[x,y] such that and is a Mathieu subspace of k[x,y].     

On spline regression under Gaussian subordination with long memory

Motivated by an example from neurobiology, we consider estimation in a spline regression model with long-range dependent errors that are generated by Gaussian subordination. Consistency and the asymptotic distribution are derived for general Hermite ranks. Simulations illustrate the asymptotic results and finite sample properties. The method is applied to optical measurements of calcium concentration in the antennal lobe of honey bees used in the study of olfactory patterns.     

Crystal structure refinement and bonding patterns of CrB4: a boron-rich boride with a framework of tetrahedrally coordinated B atoms

Crystals of chromium tetraboride, a recently proposed candidate superhard material, have been grown for the first time to allow for a first structure refinement of the compound [orthorhombic, space group Immm (No. 71), a = 474.82(8) pm, b = 548.56(8) pm, and c = 287.17(4) pm, R value (all data) = 0.018]. The previously proposed structure model is confirmed, and accurate interatomic distances are presented for the first time. First-principles electronic structure calculations emphasize the unique framework of three-dimensionally linked B atoms that are tetrahedrally coordinated and carry a slightly negative charge. All B-B bonding is of the 2-center 2-electron type. CrB(4) is metallic with a pseudogap at the Fermi level.     

Thermodynamics of CO2 adsorption on functionalized SBA-15 silica. NLDFT analysis of surface energetic heterogeneity

Siliceous SBA-15 mesoporous molecular sieves were functionalized with different amounts of 3-aminopropyl-trimethoxysilane. To obtain a more detailed insight into the material properties of the prepared samples, their textural parameters were combined with results of thermal analysis. Adsorption isotherms of carbon dioxide on parent and functionalized SBA-15 were measured in the temperature range from 273 to 333 K. From the temperature dependence of CO(2) isotherms the isosteric adsorption heats of CO(2) were determined and discussed. Information about the surface energetic heterogeneity caused by tethered 3-aminopropyl groups were obtained from CO(2) adsorption energy distributions calculated using the theoretical CO(2) adsorption isotherms derived from the non-local density functional theory. The values of isosteric heats and the energy distributions of CO(2) adsorption detect highly energetic sites and enabled quantification of their concentrations.     

Numerical solution of the two-dimensional Poincaré equation

This paper deals with numerical approximation of the two-dimensional Poincaré equation that arises as a model for internal wave motion in enclosed containers. Inspired by the hyperbolicity of the equation we propose a discretisation particularly suited for this problem, which results in matrices whose size varies linearly with the number of grid points along the coordinate axes. Exact solutions are obtained, defined on a perturbed boundary. Furthermore, the problem is seen to be ill-posed and there is need for a regularisation scheme, which we base on a minimal-energy approach.     

The time reversal operator for semigroup evolutions

A quantum theory combining an irreversible time evolution semigroup with a time reversal operator is presented.