Optimal control for lithium-ion batteries

Modelling, simulation and optimal control for a lithium-ion battery cell is discussed. The model involves ionic concentrations, currents and potentials in the electrodes and the separator together with the battery temperature as state variables. The resulting system is a nonlinear PDAE system with 10 partial, 1 ordinary differential and 4 algebraic equations involving the Butler-Volmer kinetics for describing the interaction of ionic currents and potentials. Time-optimal charging of the battery subject to age-preventing leads to a state-constrained optimal control problem which is solved in two ways. A first-discretize-then-optimize approach leads to a high-dimensional nonlinear optimization problem which is solved by an efficient solver. As an alternative, a feedback control law along an active arc of the state constraint of order 1 is derived to formulate and solve the corresponding so-called induced optimization problem. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilide Ligands

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe₃)(Dipp) (Dipp=2,6-iPr₂-C₆H₃). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)₃] (HMDS=N(SiMe₃)₂) with an excess of HN(SiMe₃)(Dipp) led to the isolation of heteroleptic [Na(HMDS)₂Fe{N(SiMe₃)Dipp}]_∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe₃)Dipp] and [Fe{N(SiMe₃)Dipp}₂] induces lateral metallation of one Me arm from the SiMe₃ group in the iron amide furnishing tetrameric [NaFe{N(SiCH₂Me₂)Dipp}{N(SiMe₃)Dipp}]₄ ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe₃)Dipp}(HMDS)Fe(C₆F₅)]_∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe₃)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.     

The Chemical Bond: When Atom Size Instead of Electronegativity Difference Determines Trend in Bond Strength

We have quantum chemically analyzed element−element bonds of archetypal H_nX−YH_n molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C−C to C−F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C−F to C−I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv?Mg(OPiv)X?n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

Thermal stability of Li2O-SiO2-CaO-P2O5-F glass

Two glasses, the first one with the composition of Li₂O·2SiO₂ and the second one with the addition of CaO, P₂O₅ and CaF₂ in the stoichiometric ratio corresponding to fluoroapatite were prepared and their tendency to crystallize has been studied by non-isothermal DTA analysis. The values of kinetic parameters calculated using the isoconversional integral method have been used to determine the temperature dependencies of both the length of isothermal induction period and the length of overall isothermal crystallization for both glasses. The estimated dependencies indicate that the glass containing CaO, P₂O₅ and CaF₂ has a lower thermal stability.     

Phosphorus donors in highly strained silicon

The hyperfine interaction of phosphorus donors in fully strained Si thin films grown on virtual Si(1-x)Ge(x) substrates with x< or =0.3 is determined via electrically detected magnetic resonance. For highly strained epilayers, hyperfine interactions as low as 0.8 mT are observed, significantly below the limit predicted by valley repopulation. Within a Green's function approach, density functional theory shows that the additional reduction is caused by the volume increase of the unit cell and a relaxation of the Si ligands of the donor.     

Spin echo MRI in the evaluation of hearts with a double outlet right ventricle: usefulness and limitations

The surgical approach to a double outlet right ventricle (DORV) is dependent on the spatial relationship of the semilunar valves, outflow tracts and ventricular septal defect (VSD). The purpose of the study was to assess the value of MRI for the evaluation of cardiovascular anatomy in patients before and after surgery for DORV. Spin echo MRI was performed in 12 patients with DORV (eight preoperative and four postoperative patients). Thin-section MRI was performed in three orthogonal planes and selected angulated views were obtained. Conventional imaging by color Doppler echocardiography and cine-angiocardiography and surgical findings, when present, served as the reference standards. The results found that the spatial relationship between semilunar valves and VSD was accurately assessed by MRI in eight out of eight preoperative patients. In the four postoperative cases MRI depicted the morphology of both outflow tracts and provided adequate information on their patency. Of the eight preoperative patients, five have undergone corrective surgery and the MRI findings were confirmed. MRI provided additional information to conventional imaging preoperatively in three cases in which the VSD opened into the outlet portion of the DORV, without there being a direct relation to a semilunar valve. In two preoperative cases in which the VSD was directly committed to the aorta, conventional imaging was conclusive. MRI was unable to depict aberrant chordae tendineae in four out of four cases. We conclude that MRI provides accurate additional anatomic information in patients with DORV, which is helpful in presurgical planning as well as during follow-up. Spin echo MRI does not visualize aberrant chordae tendineae.     

New classes of domains with explicit Bergman kernel

We introduce two classes of egg type domains, built on general bounded sym-metric domains, for which we obtain the Bergman kernel in explicit formulas. As an aux-iliary tool, we compute the integral of complex powers of the generic norm on a boundedsymmetric domains using the well-known integral of Selberg. This generalizes matrix in-tegrals of Hua and leads to a special polynomial with integer or half-integer coefficientsattached to each irreducible bounded symmetric domain.