First-Principles Characterization and Experimental Validation of the Solid-Solid Interface in a Novel Organosulfur Cathode for the Li-S Battery.

Organosulfur silanes grafted on an aluminum current collector have been proposed and demonstrated to function as a sulfur source in the cathode for a lithium-sulfur (Li-S) battery. Bis[3-(triethoxysilyl)propyl]disulfide silane (TESPD) and bis[3-(triethoxysilyl)propyl]tetrasulfide silane (TESPT) are typical examples of organosulfur complexes used for the study. These organosulfur silanes act as an insulator. Formation of polysulfides (Li2Sx), which is a major bottleneck in the case of elemental sulfur, can be eliminated using this novel cathode. In the absence of charge-carrying polysulfide species, the role of insulating TESPD/TESPT in the charge conduction pathway is an open question. Insight into the interface between the Al current collector and grafted TESPD/TESPT at an atomic level is a prerequisite for addressing the charge conduction pathway. The systematic theoretical methodology is developed based on electronic structure calculations and ab initio molecular dynamics simulations to propose the realistic cathode model (hydration environment) for the Li-S battery. A cluster model is developed to predict the reduction potentials of TESPD/TESPT disclosing the reduction reaction with Li, resulting in the intramolecular S-S bond breaking which is validated by experimental cyclic voltammetry measurements. A realistic cathode model between the aluminum current collector and TESPD/TESPT is also proposed to mimic the experimental conditions where the Al surface was exposed to O2 and H2O. The top few layers of Al are transformed into α-Al2O3 and covered with H2O molecules in the vicinity of grafted TESPD/TESPT. The structural models are further validated by comparing simulated S 2p binding energies with experimental X-ray photoelectron spectroscopy studies.

PbSe nanocrystal network formation during pyridine ligand displacement.

Solution-phase pyridine treatment displaced oleic acid capping ligands from the surface of PbSe nanocrystals. During ligand displacement the nanostructure morphology dramatically changed from well-stabilized, individual nanocrystals to form crystallographically connected nanocrystal networks. The network morphology was governed by the diameter of the constituent nanocrystals. Larger nanocrystals showed dipolar alignment but maintained individual nanocrystal character, while smaller nanocrystals crystallographically fused along the <100> axis. Optical studies of nanocrystal thin films showed that pyridine ligand displacement quenches the nanocrystal photoluminescence. Blends of nanocrystals and conjugated polymer showed photoluminescence quenching of the polymer with increasing nanocrystal content. The extent of photoluminescence quenching was only weakly dependent on the nanocrystal size or surface chemistry, suggesting that the interaction between nanocrystal and polymer is mostly in the form of energy transfer rather than charge transfer.

Ionic colloidal crystals of oppositely charged particles.

Colloidal suspensions are widely used to study processes such as melting, freezing and glass transitions. This is because they display the same phase behaviour as atoms or molecules, with the nano- to micrometre size of the colloidal particles making it possible to observe them directly in real space. Another attractive feature is that different types of colloidal interactions, such as long-range repulsive, short-range attractive, hard-sphere-like and dipolar, can be realized and give rise to equilibrium phases. However, spherically symmetric, long-range attractions (that is, ionic interactions) have so far always resulted in irreversible colloidal aggregation. Here we show that the electrostatic interaction between oppositely charged particles can be tuned such that large ionic colloidal crystals form readily, with our theory and simulations confirming the stability of these structures. We find that in contrast to atomic systems, the stoichiometry of our colloidal crystals is not dictated by charge neutrality; this allows us to obtain a remarkable diversity of new binary structures. An external electric field melts the crystals, confirming that the constituent particles are indeed oppositely charged. Colloidal model systems can thus be used to study the phase behaviour of ionic species. We also expect that our approach to controlling opposite-charge interactions will facilitate the production of binary crystals of micrometre-sized particles, which could find use as advanced materials for photonic applications.

Layer-by-layer growth of binary colloidal crystals.

We report the growth of binary colloidal crystals with control over the crystal orientation through a simple layer-by-layer process. Well-ordered single binary colloidal crystals with a stoichiometry of large (L) and small (S) particles of LS2 and LS were generated. In addition, we observed the formation of an LS3 superstructure. The structures formed as a result of the templating effect of the first layer and the forces exerted by the surface tension of the drying liquid. By using spheres of different composition, one component can be selectively removed, as is demonstrated in the growth of a hexagonal non-close-packed colloidal crystal.