Development of many-body polarizable force fields for Li-battery applications: 2. LiTFSI-doped Oligoether, polyether, and carbonate-based electrolytes

A quantum chemistry study of Li(+) interactions with ethers, carbonates, alkanes, and a trifluoromethanesulfonylimide anion (TFSI(-)) was performed at the MP2, B3LYP, and HF levels using the aug-cc-pvDz basis set for solvents and TFSI(-) anion, and [8s4p3d/5s3p2d]-type basis set for Li. A classical many-polarizable force field was developed for the LiTFSI salt interacting with ethylene carbonate (EC), gamma-butyrolactone (GBL), dimethyl carbonate (DMC), acetone, oligoethers, n-alkanes, and perfluoroalkanes. Molecular dynamics (MD) simulations were performed for EC/LiTFSI, PC/LiTFSI, GBL/LiTFSI, DMC/LiTFSI, 1,2-dimethoxyethane/LiTFSI, pentaglyme/LiTFSI, and poly(ethylene oxide) (MW = 2380)/LiTFSI electrolytes at temperatures from 298 to 423 K and salt concentrations from 0.3 to 5 M. The ion and solvent self-diffusion coefficients, electrolyte conductivity, electrolyte density, LiTFSI apparent molar volumes, and structure of the Li(+) cation environment predicted by MD simulations were found in good agreement with experimental data.     

Surface segregation of dissolved salt ions

Surface segregation of iodide, but not of fluoride or cesium ions, is observed by a combination of metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS(HeI)) of amorphous solid water exposed to CsI or CsF vapor. The same surface ionic behavior is also derived from molecular dynamics (MD) simulations of the corresponding aqueous salt solutions. The MIES results show the propensity of iodide, but not fluoride, for the surface of the amorphous solid water film, providing thus strong evidence for the suggested presence of heavier halides (iodide, bromide, and to a lesser extent chloride) at the topmost layer of aqueous surfaces. In contrast, no appreciable surface segregation of ions is observed in methanol, neither in the experiment nor in the simulation. Furthermore, the present results indicate that, as far as the thermodynamic aspects of solvation of alkali halides are concerned, amorphous solid water and methanol surfaces behave similarly as surfaces of the corresponding liquids.     

Collision-energy-resolved penning ionization electron spectroscopy of phenylacetylene and diphenylacetylene by collision with He*(2(3)s) metastable atoms

Penning ionization of phenylacetylene and diphenylacetylene upon collision with metastable He*(2(3)S) atoms was studied by collision-energy-/electron-energy-resolved two-dimensional Penning ionization electron spectroscopy (2D-PIES). On the basis of the collision energy dependence of partial ionization cross-sections (CEDPICS) obtained from 2D-PIES as well as ab initio molecular orbital calculations for the approach of a metastable atom to the target molecule, anisotropy of interaction between the target molecule and He*(2(3)S) was investigated. For the calculations of interaction potential, a Li(2(2)S) atom was used in place of He*(2(3)S) metastable atom because of its well-known interaction behavior with various targets. The results indicate that attractive potentials localize in the pi regions of the phenyl groups as well as in the pi-conjugated regions of the acetylene group. Although similar attractive interactions were also found by the observation of CEDPICS for ionization of all pi MOs localized at the C[triple bond]C bond, the in-plane regions have repulsive potentials. Rotation of the phenyl groups about the C[triple bond]C bond can be observed for diphenylacetylene because of a low torsion barrier. So the examination of measured PIES was performed taking into consideration the change of ionization energies for conjugated molecular orbitals.     

Planar graphs without triangles adjacent to cycles of length from 4 to 7 are 3-colorable

It is known that planar graphs without cycles of length from 4 to 7 are 3-colorable (Borodin et al., 2005) [13] and that planar graphs in which no triangles have common edges with cycles of length from 4 to 9 are 3-colorable (Borodin et al., 2006) [11]. We give a common extension of these results by proving that every planar graph in which no triangles have common edges with k-cycles, where k∈{4,5,7} (or, which is equivalent, with cycles of length 3, 5 and 7), is 3-colorable.     

Development of many-body polarizable force fields for Li-battery components: 1. Ether, alkane, and carbonate-based solvents

Classical many-body polarizable force fields were developed for n-alkanes, perflouroalkanes, polyethers, ketones, and linear and cyclic carbonates on the basis of quantum chemistry dimer energies of model compounds and empirical thermodynamic liquid-state properties. The dependence of the electron correlation contribution to the dimer binding energy on basis-set size and level of theory was investigated as a function of molecular separation for a number of alkane, ether, and ketone dimers. Molecular dynamics (MD) simulations of the force fields accurately predicted structural, dynamic, and transport properties of liquids and unentangled polymer melts. On average, gas-phase dimer binding energies predicted with the force field were between those from MP2/aug-cc-pvDz and MP2/aug-cc-pvTz quantum chemistry calculations.     

LiTFSI structure and transport in ethylene carbonate from molecular dynamics simulations

Molecular dynamics (MD) simulations using a many-body polarizable force field were performed on ethylene carbonate (EC) doped with lithium bistrifluoromethanesulfonamide (LiTFSI) salt as a function of temperature and salt concentration. At 313 K Li+ was coordinated by 2.7-3.2 EC carbonyl oxygen atoms and 0.67-1.05 TFSI- oxygen atoms at EC:Li = 10 and 20 salt concentrations. In completely dissociated electrolytes, however, Li+ was solvated by approximately 3.8 carbonyl oxygen atoms from EC on average. The probability of ions to participate ion aggregates decreased exponentially with an increase in the size of the aggregate. Ion and solvent self-diffusion coefficients and conductivity predicted by MD simulations were in good agreement with experiments. Approximately half of the charge was transported by charged ion aggregates with the other half carried by free (uncomplexed by counterion) ions. Investigation of the Li+ transport mechanism revealed that contribution from the Li+ diffusion together with its coordination shell to the total Li+ transport is similar to the contribution arising from Li+ exchanging solvent molecules in its first coordination shell with solvents from the outer shells.     

Distributions of the location of maximuma and minimuma for diffusions with jumps

The paper deals with methods of computation of distributions of location for maxima and minima for diffusions with jumps. As an example, we obtain explicit formulas for distributions of location for the maximum of the process which is equal to the sum of a Brownian motion and the compound Poisson process. Bibliography: 8 titles.     

The feasibility of Al-based oxide precipitation in Fe–10%Cr alloy by ion implantation

This paper reports the feasibility of nano-oxide precipitate formation in Fe–Cr alloy by ion implantation synthesis. High contents of Al⁺ and O⁺ ions were implanted into thin films of high purity Fe–10%Cr alloy at room temperature and were studied by transmission electron microscopy (TEM) and atom probe tomography (APT). In contrast, to the common two-stage implantation/annealing scheme of precipitate ensemble synthesis by ion beams, cluster formation took place at the implantation stage in our study, requiring no subsequent high-temperature annealing. The post-implantation microstructural examination revealed in the as-implanted thin foil an array of precipitates with diameters in the range of 3–30?nm. The precipitate number density distribution was found to depend on the foil thickness. The precipitate enrichment with both Al and O was confirmed by the energy-filtered TEM analysis. Judging from the electron diffraction pattern and high-resolution TEM analysis, the crystal lattice of precipitates corresponds to some cubic modification of aluminium-rich oxide or pure aluminium oxide. The precipitate lattice alignment with the host matrix was revealed for at least a part of precipitates. The analysis of APT data using cluster detection algorithm indicates the presence of local zones enriched in Al and O, even in those areas of as-implanted samples where no clusters were visible by TEM.