Li-Filled, B-Substituted Carbon Clathrates.

Inside the cages of hypothetical carbon clathrates there is precious little room, even for the smallest atoms, such as Li-unless it is the Li(+) ion that is inserted, in which case a compensating negative charge should be distributed over the carbon cage. The hypothesis explored in this paper is that Li insertion can be achieved with appropriate B substitution within the framework. The resulting structures of 2Li@C10B2 (Clathrate VII), 8Li@C38B8 (Clathrate I), 7Li@C33B7 (Clathrate IV), 6Li@C28B6 (Clathrate H), and 6Li@C28B6 (Clathrate II) are definitely stabilized in theoretical calculations, especially under elevated pressure, as judged by enthalpy criteria and bond length metrics. Different strategies for B substitution (symmetry reduction, following the parent charge distribution, and substitution on the most weakened bonds, relieving stress on bond angles) are explored. Two possible competing channels for Li doping-B substitution, formation of LiBC and C-vacancies, are investigated.

YAlC: A Bonding Chameleon with Heteropolyacetylene Features.

YAlC was prepared by a flux method. It crystallizes as a partially filled-up TlI structure, showing remarkable structural aspects at the border between Zintl phases and intermetallics. This novel ternary aluminide-carbide exhibits a unique one-dimensional multi-center bond and a polyacetylene-related aluminum carbide substructure. The different functionalities of aluminum and of yttrium are quite remarkable. While the latter behaves more like a trivalent ion, aluminum contributes considerably to covalent bonding with carbon. Still yttrium d states contribute, but hardly in a directed manner.

Seamless Rim-Functionalization of h-BN with Silica-Experiment and Theoretical Modeling.

Boron nitride contains six-ring layers, which are isostructural to graphene, and it exhibits similar extraordinary mechanical strength. Unlike graphene, hexagonal boron nitride (h-BN) is an insulator and has some polar features that make it a perfect material for those applications graphene is not suitable for, for example, purely ionic conductors, insulating membranes, transparent coatings, composite ceramics, high oxidation resistance materials. We report here a selective rim-functionalization of h-BN with SiO2 by using the Stöber process. A closed, protruding ring of SiO2 is formed covering all edges perpendicular to the [001] zones of the h-BN stacks and thus shield the most reactive centers of BN layers. SEM and HAADF-STEM images, X-ray spectroscopy, and atomic force microscopy confirm the rim-functionalization by SiO2 . XRD demonstrates the absence of any intercalation phenomenon of BN and reveals the glassy nature of the SiO2 rims. Selected variations of synthesis and theoretical modeling both confirm that rim activation by water prior to the Stöber condensation is crucial. First-principles calculations also confirm that dangling bonds of clean BN edges merge to give interlayer bonds that make further functionalization much more difficult. The reported reaction pathway should allow for other new functionalizations of pure BN and of the rimmed SiO2 /h-BN composites.

Crystal structure and electronic properties of Y3AlC3.

A novel ternary aluminum carbide, Y(3)AlC(3), has been synthesized under application of a lithium metal flux at high temperature (1523 K). Single-crystal structure determination of this compound revealed a new structure type with the Wyckoff sequence 2j3e and remarkable structural features at the border between Zintl and intermetallic phases. The puzzling bonding structure of Y(3)AlC(3) is analyzed with the aid of electronic structure calculations (energy bands and the electron localization function).

New high capacity cathode materials for rechargeable Li-ion batteries: vanadate-borate glasses.

V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO(2) glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO(2) glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods.

Simultaneous carbon coating and lithiation of oxides by contact reaction.

Chemical lithiation and carbon coating of cathode materials can lead to strongly improved electrochemical properties, especially if the active materials have low electronic conductivity. This behavior is quite often the case for new high-capacity materials. A novel synthesis method is presented in which the two processes are performed simultaneously by employing Li2C2 as both the carbon and the lithium source. In this contact reaction, the acetylide anion C2(2-) is oxidized to carbon and deposited directly on the surface of the active material, while lithium is reductively inserted into the oxidant. Two different synthesis routes are demonstrated: a tribochemical approach at room temperature and heat treatments between 150 and 600 °C. The applicability of these new carbon-coating methods are demonstrated on various crystalline and amorphous Li(x)V2O5 phases. The composites obtained were characterized by powder X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. In addition, electrochemical data confirm the chemical lithiation and show that lithiated Li(x)V2O5 with specific phases can be prepared selectively.

Characterization of LiBC by phase-contrast scanning transmission electron microscopy.

LiBC was used as a model compound for probing the applicability of phase-contrast (PC) imaging in an aberration-corrected scanning transmission electron microscope (STEM) to visualize lithium distributions. In the LiBC structure, boron and carbon are arranged to hetero graphite layers between which lithium is incorporated. The crystal structure is reflected in the PC-STEM images recorded perpendicular to the layers. The experimental images and their defocus dependence match with multi-slice simulations calculated utilizing the reciprocity principle. The observation that a part of the Li positions is not occupied is likely an effect of the intense electron beam triggering Li displacement.

Partially reduced graphite oxide as an electrode material for electrochemical double-layer capacitors.

Partially reduced graphite oxide was prepared from graphite oxide by using synthetic graphite as precursor. The reduction of graphite oxide with a layer distance of 0.57 nm resulted in a reduction of the layer distance depending on the degree of reduction. Simultaneously the amount of oxygen functionalities in the graphite oxide was reduced, which was corroborated by elemental analysis and EDX. The electrochemical activation of the partially reduced graphite oxide was investigated for tetraethylammonium tetrafluoroborate in acetonitrile and in propylene carbonate. The activation potential depends significantly on the degree of reduction, that is, on the graphene-layer distance and on the solvent used. The activation potential decreased with increasing layer distance for both positive and negative activation. The resulting capacitance after activation was found to be affected by the layer distance, the oxygen functionalities and the used electrolyte. For a layer distance of 0.43 nm and with acetonitrile as the solvent, a differential capacitance of 220 Fg(-1) was achieved for the discharge of the positive electrode near the open-circuit potential and 195 Fg(-1) in a symmetric full-cell assembly.

Niobium(V) oxynitride: synthesis, characterization, and feasibility as anode material for rechargeable lithium-ion batteries.

The decomposition reaction of niobium(V) oxytrichloride ammoniate to the oxynitride of niobium in the 5+ oxidation state was developed in a methodological way. By combining elemental analysis, Rietveld refinements of X-ray and neutron diffraction data, SEM and TEM, the sample compound was identified as approximately 5 nm-diameter particles of NbO(1.3(1))N(0.7(1)) crystallizing with baddeleyite-type structure. The thermal stability of this compound was studied in detail by thermogravimetric/differential thermal analysis and temperature-dependent X-ray diffraction. Moreover, the electrochemical uptake and release by the galvanostatic cycling method of pure and carbon-coated NbO(1.3(1))N(0.7(1)) versus lithium was investigated as an example of an Li-free transition-metal oxynitride. The results showed that reversible capacities as high as 250 and 80 A h kg(-1) can be reached in voltage ranges of 0.05-3 and 1-3 V, respectively. Furthermore, a plausible mechanism for the charge-discharge reaction is proposed.

Microstructures, surface properties, and topotactic transitions of manganite nanorods.

Manganite (gamma-MnOOH) nanorods with typical diameters of 20-500 nm and lengths of several micrometers were prepared by reacting KMnO(4) and ethanol under hydrothermal conditions. Synchrotron X-ray diffraction (XRD) reveal that the gamma-MnOOH nanorods crystallize in the monoclinic space group P2(1)/c with unit cell dimensions a = 5.2983(3) A, b = 5.2782(2) A, c = 5.3067(3) A, and beta = 114.401(2) degrees . Transmission electron microscopy shows that the gamma-MnOOH nanorods are single crystalline and that lateral attachment occurs for primary rods elongated along 101. X-ray photoelectron spectroscopy studies indicate that the surfaces of the gamma-MnOOH nanorods are hydrogen deficient and compensated by surface complexation. The Raman scattering spectrum features five main contributions at 360, 389, 530, 558, and 623 cm(-1) along with four weak ones at 266, 453, 492, and 734 cm(-1), attributed to Mn-O vibrations within MnO(6) octahedral frameworks. The structural stability of the gamma-MnOOH nanorods was discussed by means of in situ time-resolved synchrotron XRD. The monoclinic gamma-MnOOH nanorods transform into tetragonal beta-MnO(2) upon heating in air at about 200 degrees C. The reaction is topotactic and shows distinctive differences from those seen for bulk counterparts. A metastable, intermediate phase is observed, possibly connected with hydrogen release via the interstitial (1 x 1) tunnels of the gamma-MnOOH nanorods.

Oxygen self-doping in hollandite-type vanadium oxyhydroxide nanorods.

A nonaqueous liquid-phase route involving the reaction of vanadium oxychloride with benzyl alcohol leads to the formation of single-crystalline and semiconducting VO 1.52(OH) 0.77 nanorods with an ellipsoidal morphology, up to 500 nm in length and typically about 100 nm in diameter. Composition, structure, and morphology were thoroughly analyzed by neutron and synchrotron powder X-ray diffraction as well as by different electron microscopy techniques (SEM, (HR)TEM, EDX, and SAED). The data obtained point to a hollandite-type structure which, unlike other vanadates, contains oxide ions in the channels along the c-axis, with hydrogen atoms attached to the edge-sharing oxygen atoms, forming OH groups. According to structural probes and magnetic measurements (1.94 mu B/V), the formal valence of vanadium is +3.81 (V (4+)/V (3+) atomic ratio approximately 4). The experimentally determined density of 3.53(5) g/cm (3) is in good agreement with the proposed structure and nonstoichiometry. The temperature-dependent DC electrical conductivity exhibits Arrhenius-type behavior with a band gap of 0.64 eV. The semiconducting behavior is interpreted in terms of electron hopping between vanadium cations of different valence states (small polaron model). Ab initio density-functional calculations with a local spin density approximation including orbital potential (LSDA + U with an effective U value of 4 eV) have been employed to extract the electronic structure. These calculations propose, on the one hand, that the electronic conductivity is based on electron hopping between neighboring V (3+) and V (4+) sites, and, on the other hand, that the oxide ions in the channels act as electron donors, increasing the fraction of V (3+) cations, and thus leading to self-doping. Experimental and simulated electron energy-loss spectroscopy data confirm both the presence of V (4+) and the validity of the density-of-states calculation. Temperature-dependent magnetic susceptibility measurements indicate strongly frustrated antiferromagnetic interactions between the vanadium ions. A model involving the charge order of the V (3+) sites is proposed to account for the observed formation of the magnetic moment below 25 K.

Analytical evidence of amorphous microdomains within nitridosilicate and nitridoaluminosilicate single crystals.

Single crystals of new nitridosilicates and nitridoaluminosilicates with excellent R values in X-ray investigations were analysed quantitatively using 30 to 60 microm single-spot LA-ICP-MS. Significant discrepancies between expected and measured chemical composition could not be explained by the crystallographic data. High spatial resolution analysis using electron probe microanalysis (EPMA, 10 microm) leads to the discovery of inhomogeneities in the crystalline material. The application of standard single-spot LA-ICP-MS with a spatial resolution of 30 to 60 microm is not suitable for the analysis of these crystals as the existing inhomogeneities dominate and alter the determined concentrations. However, owing to the better detection capabilities, a scanning LA-ICP-MS procedure enables a more representative analysis of single crystals of Ca(5)Si(2)Al(2)N(8) than single-spot LA-ICP-MS as a result of a larger sampling volume. It is highly likely that these impurities consist of amorphous, vitreous phases as powder diffraction X-ray data indicates the existence of a significant fraction of an X-ray amorphous material besides crystalline silicates. These microdomains contain less aluminium, silicon and calcium or are nearly free of aluminium, which explains the detected discrepancies in the chemical composition.

Oxidic nanotubes and nanorods--anisotropic modules for a future nanotechnology.

The discovery of carbon nanotubes in 1991 is a milestone in nanomaterials research. Since then, more and more anisotropic nanoparticles have been detected and characterized. The development of nanodevices might benefit from the distinct morphology and high aspect ratio of nanorods and nanotubes as these can be functionalized in unique ways such as incorporation of nanorods in nanotubes. Downscaling a broad range of materials to 1D nanoscopic structures is currently the focus of a rapidly growing scientific community. Developing general pathways to this goal would transfer a wide variety of properties to the nanoscale-a spectrum of phenomena so diverse that it would cover not only inorganic systems but all of materials science. Synthesis of real functional materials, however, always involves considerable synthetic ingenuity, interdisciplinary collaboration, as well as technological and economical realism. The major topic of this review is to provide a survey of recent progress in the synthesis of oxidic nanotubes and nanorods-with their non-oxidic counterparts briefly highlighted-and to outline the major synthetic routes leading to them. With the challenges of synthesizing bulk oxidic materials in mind, the establishment of trustworthy and uncomplicated ways of providing them as anisotropic nano-modules on an industrial scale appears to be more or less serendipity. Of the methods utilized in nanotube and nanorod synthesis solvothermal processes have emerged as powerful tools for generalizing and systematizing controlled syntheses of nano-morphologies. The flexibility and reliability of this synthetic approach is demonstrated here for the transformation of transition-metal oxides into high-quality anisotropic nanomaterials.

Chemical Twinning in Zintl Phases.

In the systems Ba/Mg/(Si, Ge), two new ternary Zintl phases with the compositions BaMg(4)Si(3) and BaMg(4)Ge(3) were found and structurally characterized. Both compounds are isotypic and crystallize with a new structure type [BaMg(4)Si(3), P4/mmm, Z = 1, a = 4.6115(9) Å, c = 8.615(2) Å; BaMg(4)Ge(3), P4/mmm, Z = 1, a = 4.6335(8) Å, c = 8.746(2) Å]. The anionic partial structure is built of X(2)(6)(-) dumbbells and isolated X(4)(-) ions (X = Si, Ge), and the structure can be described according to the Zintl-Klemm-Busmann concept with the formulation (Ba(2+))(Mg(2+))(4)[X(2)(6)(-)][X(4)(-)]. The BaMg(4)X(3) structure can also be described as a result of the fusion of the structures of Mg(2)X and BaMg(2)X(2). In this regard, BaMg(4)Si(3) and BaMg(4)Ge(3) are very striking examples of chemical twinning.

Redox-Active Nanotubes of Vanadium Oxide.

Unlike many small carbon nanotubes, VOx nanotubes (shown on the right) are obtained as the main product of a direct chemical synthesis at relatively low temperatures. The multiwalled material contains template molecules between the individual shells, which by a simple cation exchange can be removed without destruction of the tubes.

A Naphthalene-Like Si1010- Unit in the Novel ∞2 [Si2030- ] Planar Anion of Sr13 Mg2 Si20.

Two interpenetrating 2∞ [Si2030- ] polyanions with naphthalene-like Si1010- building blocks (see picture) characterize the"nonclassical" Zintl phase Sr13 Mg2 Si20 , which is formed from the elements at 1230-1240 K. The ecliptical stacking of the Si1010- units leads to one-dimensional conductivity along the stacking direction.