Synergistically Enhanced Polysulfide Chemisorption Using a Flexible Hybrid Separator with N and S Dual-Doped Mesoporous Carbon Coating for Advanced Lithium-Sulfur Batteries.

Because of the outstanding high theoretical specific energy density of 2600 Wh kg(-1), the lithium-sulfur (Li-S) battery is regarded as a promising candidate for post lithium-ion battery systems eligible to meet the forthcoming market requirements. However, its commercialization on large scale is thwarted by fast capacity fading caused by the Achilles' heel of Li-S systems: the polysulfide shuttle. Here, we merge the physical features of carbon-coated separators and the unique chemical properties of N and S codoped mesoporous carbon to create a functional hybrid separator with superior polysulfide affinity and electrochemical benefits. DFT calculations revealed that carbon materials with N and S codoping possess a strong binding energy to high-order polysulfide species, which is essential to keep the active material in the cathode side. As a result of the synergistic effect of N, S dual-doping, an advanced Li-S cell with high specific capacity and ultralow capacity degradation of 0.041% per cycle is achieved. Pushing our simple-designed and scalable cathode to a highly increased sulfur loading of 5.4 mg cm(-2), the Li-S cell with the functional hybrid separator can deliver a remarkable areal capacity of 5.9 mAh cm(-2), which is highly favorable for practical applications.

Probing the interactions of phenol with oxygenated functional groups on curved fullerene-like sheets in activated carbon.

The mechanism(s) of interactions of phenol with oxygenated functional groups (OH, COO and COOH) in nanopores of activated carbon (AC) is a contentious issue among researchers. This mechanism is of particular interest because a better understanding of the role of such groups in nanopores would essentially translate to advances in AC production and use, especially in regard to the treatment of organic-based wastewaters. We therefore attempt to shed more light on the subject by employing density functional theory (DFT) calculations in which fullerene-like models integrating convex or concave structure, which simulate the eclectic porous structures on AC surface, are adopted. TEM analysis, EDS mapping and Boehm titration are also conducted on actual phenol-adsorbed AC. Our results suggest the widely-reported phenomenon of decreased phenol uptake on AC due to increased concentration of oxygenated functional groups is possibly attributed to the increased presence of the latter on the convex side of the curved carbon sheets. Such a system effectively inhibits phenol from getting direct contact with the carbon sheet, thus constraining any available π-π interaction, while the effect of groups acting on the concave part of the curved sheet does not impart the same detriment.

Stimuli-responsive nanogel composites and their application in nanomedicine.

Nanogels are nanosized crosslinked polymer networks capable of absorbing large quantities of water. Specifically, smart nanogels are interesting because of their ability to respond to biomedically relevant changes like pH, temperature, etc. In the last few decades, hybrid nanogels or composites have been developed to overcome the ever increasing demand for new materials in this field. In this context, a hybrid refers to nanogels combined with different polymers and/or with nanoparticles such as plasmonic, magnetic, and carbonaceous nanoparticles, among others. Research activities are focused nowadays on using multifunctional hybrid nanogels in nanomedicine, not only as drug carriers but also as imaging and theranostic agents. In this review, we will describe nanogels, particularly in the form of composites or hybrids applied in nanomedicine.

SEI-component formation on sub 5 nm sized silicon nanoparticles in Li-ion batteries: the role of electrode preparation, FEC addition and binders.

Silicon is a promising negative electrode for secondary lithium-based batteries, but the electrochemical reversibility of particularly nanostructured silicon electrodes drastically depends on their interfacial characteristics, commonly known as the solid electrolyte interface (SEI). The beneficial origin of certain electrolyte additives or different binders is still discussed controversially owing to the challenging peculiarities of interfacial post-mortem investigations of electrodes. In this work, we address the common difficulties of SEI investigations of porous silicon/carbon nanostructures and study the addition of a fluoroethylene carbonate (FEC) as a stabilizing additive as well as the use of two different binders, carboxymethyl cellulose/styrene-butadiene rubber (CMC/SBR) and polyacrylic acid (PAA), for the SEI formation. The electrode is composed of silicon nanocrystallites below 5 nm diameter allowing a detailed investigation of interfacial characteristics of silicon owing to the high surface area. We first performed galvanostatic long-term cycling (400 times) and carried out comprehensive ex situ characterization of the cycled nanocrystalline silicon electrodes with XRD, EDXS, TEM and XPS. We modified the preparation of the electrode for post-mortem characterization to distinguish between electrolyte components and the actual SEI. The impact of the FEC additive and two different binders on the interfacial layer is studied and the occurrence of diverse compounds, in particular LiF, Li2O and phosphates, is discussed. These results help to understand general issues in SEI formation and to pave the way for the development of advanced electrolytes allowing for a long-term performance of nanostructured Si-based electrodes.

A direct and quantitative three-dimensional reconstruction of the internal structure of disordered mesoporous carbon with tailored pore size.

A new technique that allows direct three-dimensional (3D) investigations of mesopores in carbon materials and quantitative characterization of their physical properties is reported. Focused ion beam nanotomography (FIB-nt) is performed by a serial sectioning procedure with a dual beam FIB-scanning electron microscopy instrument. Mesoporous carbons (MPCs) with tailored mesopore size are produced by carbonization of resorcinol-formaldehyde gels in the presence of a cationic surfactant as a pore stabilizer. A visual 3D morphology representation of disordered porous carbon is shown. Pore size distribution of MPCs is determined by the FIB-nt technique and nitrogen sorption isotherm methods to compare both results. The obtained MPCs exhibit pore sizes of 4.7, 7.2, and 18.3 nm, and a specific surface area of ca. 560 m(2)/g.

Functionalised conjugated materials as building blocks of electronic nanostructures.

Two different approaches towards conjugated material (carbon nanotubes, conjugated polymers) functionalisation are presented: covalent bonding of functional groups and covalent interaction with soluble polymers. Covalent functionalisation of carbon nanotubes is made by reaction of the aromatic ring with aryl radicals, produced by reduction of diazonium ions. In the case of conducting polymers, covalent functionalisation is brought about by reaction of polyanilines with diazotized aromatic amines (including amino terminated azo dyes). The non covalent functionalisation of carbon nanotubes is made by wrapping the nanotubes with soluble conducting polyanilines. The functionalised materials are characterised by FTIR spectroscopy, X-ray diffraction, dynamic light scattering, ultraviolet-visible absorption and emission spectroscopy, transmission electron microscopy, cyclic voltammetry, differential electrochemical mass spectroscopy and conductivity measurements. The materials are to build ionic self assembled multilayers using a layer-by-layer deposition process. The charge transport and electrocatalytic behaviour of the assemblies, relevant to the application of the assemblies in nanostructured electrochemical biosensors, are evaluated using different redox molecules and/or its intrinsic electroactivity as probes.