A Hydrostable Cathode Material Based on the Layered P2@P3 Composite that Shows Redox Behavior for Copper in High‐Rate and Long‐Cycling Sodium‐Ion Batteries

Low‐cost layered oxides free of Ni and Co are considered to be the most promising cathode materials for future sodium‐ion batteries. Biphasic Na_0.78Cu_0.27Zn_0.06Mn_0.67O₂ obtained via superficial atomic‐scale P3 intergrowth with P2 phase induced by Zn doping, consisting of inexpensive transition metals, is a promising cathode for sodium‐ion batteries. The P3 phase as a covering layer in this composite shows not only in excellent electrochemical performance but also its tolerance to moisture. The results indicate that partial Zn substitutes can effectively control biphase formation for improving the structural/electrochemical stability as well as the ionic diffusion coefficient. Based on in situ synchrotron X‐ray diffraction coupled with electron‐energy‐loss spectroscopy, a possible Cu^2+/3+ redox reaction mechanism has now been revealed.     

Morphology and Phase Composition of Particles Produced by Electro-Discharge-Machining of Iron

Towards producing metallic particles of controlled size and spherical shape, which are of technological importance, we have collected in the filters of an electro-discharge-machine (EDM) the material ejected from the surface of EDM iron pieces. The conditions of machining were varied for kerosene and water as dielectrics, using a discharge current of 25 A and duration times of 16 and 3072 μs for kerosene and of 32, 384 and 768 μs for water, respectively. Scanning electron microscopy was used to assess the effect of the time of discharge on the size of the particles. Mössbauer spectroscopy and X-ray diffraction revealed that for kerosene EDM particles only cementite-like carbides of diverse stoichiometry were formed. While no oxide was found for kerosene spheres, the analyses showed that besides the main fraction of α-Fe, a small percentage of wüstite (and traces of hematite for the 384 μs sample) formed on the water EDM ones.     

Possibility and Time in Quantum Mechanics

In the discourse of quantum mechanics it is usual to say that non-commuting observables cannot have definite values at the same time, or that they cannot be simultaneously measured. But, what does the term ‘cannot’ mean in this context? Does it stand for impossible? Should Heisenberg’s principle be read in terms of uncertainty or of indeterminacy? On the other hand, whereas the debates about the nature of time in classical and relativistic mechanics have been many and varied, the question about the nature of time in quantum mechanics has not received the same attention, especially when compared to the large amount of literature on interpretive issues. The purpose of this paper is to show that, under a realist interpretation of quantum mechanics, these two matters, possibility and time, are strongly related. The final aim is to argue that, when possibility and actuality are conceived as irreducible modes of being, they are correlated to two different notions of time that can be distinguished in the quantum realm: parameter-time and event-time.     

Manipulating Layered P2@P3 Integrated Spinel Structure Evolution for High-Performance Sodium-Ion Batteries

Structural evolution of the cathode during cycling plays a vital role in the electrochemical performance of sodium-ion batteries. A strategy based on engineering the crystal structure coupled with chemical substitution led to the design of the layered P2@P3 integrated spinel oxide cathode Na_0.5Ni_0.1Co_0.15Mn_0.65Mg_0.1O₂, which shows excellent sodium-ion half/full battery performance. Combined analyses involving scanning transmission electron microscopy with atomic resolution as well as in situ synchrotron-based X-ray absorption spectra and in situ synchrotron-based X-ray diffraction patterns led to visualization of the inherent layered P2@P3 integrated spinel structure, charge compensation mechanism, structural evolution, and phase transition. This study provides an in-depth understanding of the structure-performance relationship in this structure and opens up a novel field based on manipulating structural evolution for the design of high-performance battery cathodes.     

Li intercalation and anion/cation substitution of transition metal chalcogenides: Effects on crystal structure,microstructure, magnetic properties and Li+ ion mobility

We investigated experimentally the effect of Li intercalation on the structural, microstructural and magnetic properties as well as on the Li ion diffusivity of the complex chalcogenides Cr_5?yTi_ySe₈. In addition, the effect of anion substitution in TiS_2?zSe_z on the Li diffusion parameters was studied by ⁷Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements.For Cr_5?yTi_ySe₈ the Li⁺ insertion is accompanied by an irreversible phase transition from monoclinic to trigonal symmetry which is electronically driven. The maximal Li content in the host material depends on the Ti content and decreases with increasing y in Cr_5?yTi_ySe₈. The intercalated materials can be deintercalated and the minimal Li content in the residual compound increases with Ti abundance. The intercalation process is accompanied by drastic changes of the microstructure. Electrochemical discharge curves depend significantly on the Ti. According to the results of XANES investigations performed on Cr₄TiSe₈, Ti is first reduced during Li uptake and Cr atoms accept electrons at later stages of the intercalation reaction. In-situ energy dispersive X-ray diffraction experiments show that the Li intercalation at room temperature proceeds via two different mechanisms while intercalation at 60 °C is faster and is dominated by one mechanism. ⁷Li MAS NMR measurements revealed a variety of transition metal environments around the Li sites corresponding to the Cr/Ti disorder. The NMR studies also indicate fast Li dynamics. The magnetism of the educts is dominated by strong antiferromagnetic exchange interactions in the high temperature region and by spin-glass behavior in the low temperature range. Intercalation of Li weakens the antiferromagnetic exchange and for fully intercalated materials ferromagnetic exchange is observed. The interpretation of the experimental results is supported by accompanying band structure calculations.In layer-structured Li_xTiS_2?zSe_z (x ≈ 0.7) the Li diffusivity was investigated by various NMR techniques and compared with results obtained for the pure end members Li_xTiS₂ and Li_xTiSe₂. In particular, anion substitution clearly influences the slopes of the low-T flanks of the diffusion induced NMR relaxation-rate peaks. The corresponding activation barriers characterizing local hopping processes are reduced in the mixed samples with 0 < z < 2 and can be explained by a domain model. DFT calculations yield very small hopping barriers along S-rich and Se-rich domain boundaries while the barriers for Li migration inside the domains are rather high. It is therefore assumed that Li migrates along the domain boundaries.     

Experimental investigation of the effect of Reynolds number on flow structures in the wake of a circular parachute canopy

In the present study, an experimental study was conducted to characterize the effect of Reynolds number on flow structures in the turbulent wake of a circular parachute canopy by utilizing stereoscopic particle image velocime- try （Stereo-PIV） technique. The parachute model tested in the present study was attached by 28 nylon suspension lines and placed horizontally at the test section center of the wind tunnel. The obtained results showed that with the in- crease of Reynolds number, the intensities of the vortices near the downstream region of the canopy skirt were found to increase accordingly. However, the increase of Reynolds number did not result in a significant change in ensemble- averaged normalized x-component of the velocity, ensembleaveraged normalized vorticity, normalized Reynolds stress, and normalized turbulent kinetic energy distributions in the turbulent wake of the circular parachute canopy. The obtained results are very useful to further our understanding about the unsteady aerodynamics in the wake of flexible circular parachute canopies and to constitute a reference for CFD computation.     

Sampling configurations in Monte Carlo simulations for quantum mechanical studies of solvent effects

Discrete models obtained from computer simulation are in increase use to study solvent effects. The approach consists of generating supermolecular structures for quantum mechanical calculations. The properties of the solute are calculated as an ensemble average over configurations generated by the simulation. An analysis of the efficiency of the simulation shows that the number of configurations necessary for the ensemble average can be reduced drastically. As an application to solvatochromism, the calculated spectral shift of the ¹B_2u(π − π*) transition of benzene in water is shown to be the same whether it is calculated with many but correlated configurations or with just a few uncorrelated configurations. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 249–253, 1998     

Asequential Monte Carlo quantum mechanics study of the hydrogen-bond interaction and the solvatochromic shift of the n-pi* transition of acrolein in water

The sequential Monte Carlo (MC) quantum mechanics (QM) methodology, using time-dependent density-functional theory (TD-DFT), is used to study the solvatochromic shift of the n-pi* transition of trans-acrolein in water. Using structures obtained from the isothermal-isobaric Metropolis MC simulation TD-DFT calculations, within the B3LYP functional, are performed for the absorption spectrum of acrolein in water. In the average acrolein makes one hydrogen bond with water and the hydrogen-bond shell is responsible for 30% of the total solvatochromic shift, considerably less than the shift obtained for the minimum-energy configurations. MC configurations are sampled after analysis of the statistical correlation and 100 configurations are extracted for subsequent QM calculations. All-electron TD-DFT B3LYP calculations of the absorption transition including acrolein and all explicit solvent molecules within the first hydration shell, 26 water molecules, give a solvatochromic shift of 0.18 +/- 0.11 eV. Using simple point charges to represent the solvent the shifts are calculated for the first, second, and third solvation shells. The results converge for the calculated shift of 0.20 +/- 0.10 eV in very good agreement with the experimentally inferred result of 0.20 +/- 0.05 eV. All average results presented are statistically converged.