Crystal structures, microtopography, morphologies, elemental compositions, and ionic conductivity have been investigated for Li5-xLa3(Nb,Ta)O12-y using X-ray diffraction (XRD), field-emission analytical scanning and transmission electron microscopies (S/TEM), and electrochemical impedance spectroscopy. Using Rietveld refinements with powder XRD patterns, we determined that the number of Li atoms in the formula is less than 5 and that Li5-xLa3(NbTa)O12-y crystallizes in the cubic garnet structure with a space group Ia-3d. Sintering at varying temperatures (750–1000 °C) for 5 h in an ambient atmosphere produced distinct outcomes. Rietveld refinements disclosed that the sample sintered at 1000 °C (Li3.43(2)La3Nb1.07(2)Ta0.93(2)O12-y, a = 12.8361(7) Å, V = 2114.96(3) Å3) exhibited the highest ionic conductivity, while the 850 °C sample had the lowest conductivity, characterized by lower Li concentration and impurity phases (Li(Nb,Ta)3O88, Li2CO3). Analyses, including XRD and electron microscopy, confirmed the 1000 °C sample as a relatively phase pure with enhanced Li content (Li/La = 1.2), larger grains (15 μm), and uniform crystallinity. The 1000 °C sample introduced additional partially filled Li3 (96h) sites, promoting Li migration, and enhancing ionic conductivity. The resulting XRD pattern at 1000 °C has been submitted to the Powder Diffraction File as a reference.

Poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymers synthesized via inverse vulcanization represent an emerging class of electrochemically active polymers recently used in cathodes for Li–S batteries, capable of realizing enhanced capacity retention (1,005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. The composite cathodes are organized in complex hierarchical three-dimensional (3D) architectures, which contain several components and are challenging to understand and characterize using any single technique. Here, multimode analytical scanning and transmission electron microscopies and energy-dispersive X-ray/electron energy-loss spectroscopies coupled with multivariate statistical analysis and tomography were applied to explore origins of the cathode-enhanced capacity retention. The surface topography, morphology, bonding, and compositions of the cathodes created by combining sulfur copolymers with varying 1,3-diisopropenylbenzene content and conductive carbons have been investigated at multiple scales in relation to the electrochemical performance and physico-mechanical stability. We demonstrate that replacing the elemental sulfur with organosulfur copolymers improves the compositional homogeneity and compatibility between carbons and sulfur-containing domains down to sub-5 nm length scales resulting in (a) intimate wetting of nanocarbons by the copolymers at interfaces; (b) the creation of 3D percolation networks of conductive pathways involving graphitic-like outer shells of aggregated carbons; (c) concomitant improvements in the stability with preserved meso- and nanoscale porosities required for efficient charge transport.

Poly[sulfur-random-1,3-diisopropenylbenzene (DIB)] copolymers synthesized via inverse vulcanization form electrochemically active polymers used as cathodes for high-energy density Li–S batteries, capable of enhanced capacity retention (1005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. In this prospective, we demonstrate how analytical electron microscopy can be employed as a powerful tool to explore the origins of the enhanced capacity retention. We analyze morphological and compositional features when the copolymers, with DIB contents up to 50% by mass, are blended with carbon nanoparticles. Replacing the elemental sulfur with the copolymers improves the compatibility and interfacial contact between active sulfur compounds and conductive carbons. There also appears to be improvements of the cathode mechanical stability that leads to less cracking but preserving porosity. This compatibilization scheme through stabilized organosulfur copolymers represents an alternative strategy to the nanoscale encapsulation schemes which are often used to improve the cycle life in high-energy density Li–S batteries.

A functionalization method for the specific and selective immobilization of the streptavidin (SA) protein on semiconductor nanowires (NWs) was developed. Silicon (Si) and silicon carbide (SiC) NWs were functionalized with 3-aminopropyltriethoxysilane (APTES) and subsequently biotinylated for the conjugation of SA. Existence of a thin native oxide shell on both Si and SiC NWs enabled efficient binding of APTES with the successive attachment of biotin and SA as was confirmed with x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and atomic force microscopy. Fluorescence microscopy demonstrated nonspecific, electrostatic binding of the SA and the bovine serum albumin (BSA) proteins to APTES-coated NWs. Inhibition of nonspecific BSA binding and enhancement of selective SA binding were achieved on biotinylated NWs. The biofunctionalized NWs have the potential to be used as biosensing platforms for the specific and selective detection of proteins.

Extended abstract of a paper presented at the Pre-Meeting Congress: Materials Research in an Aberration-Free Environment, at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, July 31 and August 1, 2004.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Measuring material properties is critical to understanding the behavior of contemporary nanostructured materials. In this paper, we show that as a consequence of the universal binding energy relation (UBER), universal features and strong scaling correlations exist between the volume plasmon energy and cohesive energy, valence electron density, elastic constants and hardness of various materials with metallic and covalent bonding. Based on these relations, we propose novel techniques that allow direct measurement and imaging of material properties in situ using valence electron energy-loss spectroscopy combined with energy-filtering transmission electron microscopy. This is illustrated by evaluation of elastic and cohesive properties of individual metastable nanoprecipitates in structural alloys and hardness of diesel-engine soot particles. The results demonstrate that new plasmon spectro-microscopic techniques have the potential to determine quantitatively and image multiple solid-state properties at the nanoscale, establishing a new capability for material research.