A transferable force-field for alkali metal nitrates

We present a new rigid-ion force-field for the alkali metal nitrates that is suitable for simulating solution chemistry, crystallisation and polymorphism. We show that it gives a good representation of the crystal structures, lattice energies, elastic and dielectric properties of these compounds over a wide range of temperatures. Since all the alkali metal nitrates are fitted together using a common model for the nitrate anion, the force-field is also suitable for simulating solid solutions. We use the popular Joung and Cheatham model for the interactions of the alkali metal cations with water and obtain the interaction of the nitrate ion with water by fitting to a hydrate

Design parameters for ionic liquid–molecular solvent blend electrolytes to enable stable Li metal cycling within Li–O2 batteries

Effective utilization of Li-metal electrodes is vital for maximizing the specific energy of lithium–oxygen (Li–O2) batteries. Many conventional electrolytes that support Li–O2 cathode processes (e.g., dimethyl sulfoxide, DMSO) are incompatible with Li-metal. Here, a wide range of ternary solutions based on solvent, salt, and ionic liquid (IL) are explored to understand how formulations may be tailored to enhance stability and performance of DMSO at Li-metal electrodes. The optimized formulations therein facilitate stable Li plating/stripping performances, Columbic efficiencies >94%, and improved performance in Li–O2 full cells. Characterization of Li surfaces reveals the suppression of dendritic deposition and corrosion and the modulation of decomposition reactions at the interface within optimized formulations. These observations are correlated with spectroscopic characterization and simulation of local solvation environments, indicating the persistent importance of DMSO–Li+-cation interactions. Therein, stabilization remains dependent on important molar ratios in solution and the 4:1 solvent-salt ratio, corresponding to ideal coordination spheres in these systems, is revealed as critical for these ternary formulations. Importantly, introducing this stable, non-volatile IL has negligible disrupting effects on the critical stabilizing interactions between Li+ and DMSO and, thus, may be carefully introduced to tailor other key electrolyte properties for Li–O2 cells

Evaluation of correlated studies using liquid cell‐ and cryo‐transmission electron microscopy : hydration of calcium sulfate and the phase transformation pathways of bassanite to gypsum

Insight into the nucleation, growth and phase transformations of calcium sulfate could improve the performance of construction materials, reduce scaling in industrial processes and aid understanding of its formation in the natural environment. Recent studies have suggested that the calcium sulfate pseudo polymorph, gypsum (CaSO4·2H2O) can form in aqueous solution via a bassanite (CaSO4·0.5H2O) intermediate. Some in situ experimental work has also suggested that the transformation of bassanite to gypsum can occur through an oriented assembly mechanism. In this work, we have exploited liquid cell transmission electron microscopy (LCTEM) to study the transformation of bassanite to gypsum in an undersaturated aqueous solution of calcium sulfate. This was benchmarked against cryogenic TEM (cryo-TEM) studies to validate internally the data obtained from the two microscopy techniques. When coupled with Raman spectroscopy, the real-time data generated by LCTEM, and structural data obtained from cryo-TEM show that bassanite can transform to gypsum via more than one pathway, the predominant one being dissolution/reprecipitation. Comparisons between LCTEM and cryo-TEM also show that the transformation is slower within the confined region of the liquid cell as compared to a bulk solution. This work highlights the important role of a correlated microscopy approach for the study of dynamic processes such as crystallisation from solution if we are to extract true mechanistic understanding

Electron transparent nanotubes reveal crystallization pathways in confinement

The cylindrical pores of track-etched membranes offer excellent environments for studying the effects of confinement on crystallization as the pore diameter is readily varied and the anisotropic morphologies can direct crystal orientation. However, the inability to image individual crystals in situ within the pores in this system has prevented many of the underlying mechanisms from being characterized. Here, we study the crystallization of calcium sulfate within track-etched membranes and reveal that oriented gypsum forms in 200 nm diameter pores, bassanite in 25–100 nm pores and anhydrite in 10 nm pores. The crystallization pathways are then studied by coating the membranes with an amorphous titania layer prior to mineralization to create electron transparent nanotubes that protect fragile precursor materials. By visualizing the evolutionary pathways of the crystals within the pores we show that the product single crystals derive from multiple nucleation events and that orientation is determined at early reaction times. Finally, the transformation of bassanite to gypsum within the membrane pores is studied using experiment and potential mean force calculations and is shown to proceed by localized dissolution/reprecipitation. This work provides insight into the effects of confinement on crystallization processes, which is relevant to mineral formation in many real-world environments

A giant reconstruction of α-quartz (0001) interpreted as three domains of nano dauphine twins

Silica (SiO2) is one of the most common materials on Earth. The crystalline form α-quartz is the stable silica polymorph at ambient conditions although metastable forms exist. α-quartz is a piezoelectric material, it can be produced artificially and is widely used for example in electronics and the biosciences. Despite the many application areas, the atomic surface structures of silica polymorphs are neither well understood nor well characterized. Here we present measurements of α-quartz (0001). Helium Atom Scattering combined with Atomic Force Microscopy reveals a giant reconstruction consisting of 5.55 ± 0.07 nm wide ribbons, oriented 10.4° ± 0.8° relative to the bulk unit cell. The ribbons, with the aid of atomistic modelling, can be explained as a self-organised pattern of nano Dauphine twins (nano electrical twins)

Ba 6−3x Nd 8+2x Ti 18 O 54 Tungsten Bronze A New High-Temperature n-Type Oxide Thermoelectric

International audienceSemiconducting Ba 6−3x Nd 8+2x Ti 18 O 54 ceramics (with x = 0.00 to 0.85) were synthesized by the mixed oxide route followed by annealing in a reducing atmosphere; their high-temperature thermoelectric properties have been investigated. In conjunction with the experimental observations, atomistic simulations have been performed to investigate the anisotropic behavior of the lattice thermal conductivity. The ceramics show promising n-type thermoelectric properties with relatively high Seebeck coefficient, moderate electrical conductivity, and temperature-stable, low thermal conductivity; For example, the composition with x = 0.27 (i.e., Ba 5.19 Nd 8.54 Ti 18 O 54 ) exhibited a Seebeck coefficient of S 1000K  = 210 µV/K, electrical conductivity of σ 1000K  = 60 S/cm, and thermal conductivity of k 1000K  = 1.45 W/(m K), leading to a ZT value of 0.16 at 1000 K. © 2015, The Author(s)