Lithium metal is known to possess a very high theoretical capacity of 3,842 mAh g À 1 in lithium batteries. However, the use of metallic lithium leads to extensive dendritic growth that poses serious safety hazards. Hence, lithium metal has long been replaced by layered lithium metal oxide and phospho-olivine cathodes that offer safer performance over extended cycling, although significantly compromising on the achievable capacities. Here we report the defect-induced plating of metallic lithium within the interior of a porous graphene network. The network acts as a caged entrapment for lithium metal that prevents dendritic growth, facilitating extended cycling of the electrode. The plating of lithium metal within the interior of the porous graphene structure results in very high specific capacities in excess of 850 mAh g À 1 . Extended testing for over 1,000 charge/discharge cycles indicates excellent reversibility and coulombic efficiencies above 99%.

Because of their abundance, sodium and calcium can be attractive in ion batteries for large-scale grid storage. However, many of the anode materials being pursued have limitations including volume expansion, lack of passivating films, and slow kinetics. Here, we investigate the adsorption of Na and Ca on graphene with divacancy and Stone-Wales defects in graphene. Our results show that although adsorption of Na and Ca is not possible on pristine graphene, enhanced adsorption is observed on defective graphene because of increased charge transfer between the adatoms and defects. We find that the capacity of graphene increases with the density of the defects. For the maximum possible divacancy defect densities, capacities of 1450 and 2900 mAh/g for Na- and Ca-ion batteries, respectively, can be achieved. For Stone-Wales defects, we find maximum capacities of 1071 and 2142 mAh/g for Na and Ca, respectively. Our results provide guidelines to create better high-capacity anode materials for Na- and Ca-ion batteries.

In a wavelength-routed optical network, a transmitted signal remains in the optical domain over the entire route (lightpath) assigned to it between its source and destination nodes. The optical signal may have to traverse a number of crossconnect switches (XCS's), fiber segments, and optical amplifiers, e.g., erbium-doped fiber amplifiers (EDFA's). Thus, while propagating through the network, the signal may degrade in quality as it encounters crosstalk at the XCS's and also picks up amplified spontaneous emission (ASE) noise at the EDFA's. Since these impairments continue to degrade the signal quality as it progresses toward its destination, the received bit error rate (BER) at the destination node might become unacceptably high. Previous work on the lightpath routing and wavelength assignment (RWA) problem assumed an ideal physical layer and ignored these transmission impairments. The main contribution of our work is to incorporate the role of the physical layer in setting up lightpaths by employing appropriate models of multiwavelength optical devices (XCS's and EDFA's) such that the BER of a candidate lightpath can be computed, in advance, to determine if this lightpath should be used for the call. Features from existing RWA algorithms are integrated with our on-line BER calculation mechanism. Our simulation studies indicate that employing BER-based call-admission algorithms has a significant impact on the performance of realistic networks.

Water microdroplets containing graphene oxide and a second solute are shown to spontaneously segregate into sack-cargo nanostructures upon drying. Analytical modelling and molecular dynamics suggest the sacks form when slow-diffusing graphene oxide preferentially accumulates and adsorbs at the receding air-water interface, followed by capillary collapse. Cargo-filled graphene nanosacks can be nanomanufactured by a simple, continuous, scalable process and are promising for many applications where nanoscale materials should be isolated from the environment or biological tissue.

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We report a study of the self-assembly of 1,4-benzenedimethanethiol monolayers on gold formed in n-hexane solution held at 60 °C for 30 min and in dark conditions. The valence band characteristics, the thickness of the layer, and the orientation of the molecules were analyzed at a synchrotron using high resolution photoelectron spectroscopy and near edge X-ray adsorption spectroscopy. These measurements unambiguously attest the formation of a single layer with molecules arranged in the upright position and presenting a free -SH group at the outer interface. Near edge X-ray absorption fine structure (NEXAFS) measurements suggest that the molecular axis is oriented at 24° with respect to the surface normal. In addition, valence band features could be successfully associated to specific molecular orbital contributions thanks to the comparison with theoretically calculated density of states projected on the different molecular units.

Many environmental technologies rely on containment by engineered barriers that inhibit the release or transport of toxicants. Graphene is a new, atomically thin, two-dimensional sheet material, whose aspect ratio, chemical resistance, flexibility, and impermeability make it a promising candidate for inclusion in a next generation of engineered barriers. Here we show that ultrathin graphene oxide (GO) films can serve as effective barriers for both liquid and vapor permeants. First, GO deposition on porous substrates is shown to block convective flow at much lower mass loadings than other carbon nanomaterials, and can achieve hydraulic conductivities of 5×10−12 cm/s or lower. Second we show that ultrathin GO films of only 20 nm thickness coated on polyethylene films reduce their vapor permeability by 90% using elemental mercury as a model vapor toxicant. The barrier performance of GO in this thin-film configuration is much better than the Nielsen model limit, which describes ideal behavior of flake-like fillers uniformly imbedded in a polymer. The Hg barrier performance of GO films is found to be sensitive to residual water in the films, which is consistent with molecular dynamics (MD) simulations that show lateral diffusion of Hg atoms in graphene interlayer spaces that have been expanded by hydration.

Silicon is a high-capacity anode material for lithium-ion batteries. Electrochemical cycling of Si electrodes usually produces amorphous Li x Si (a-Li x Si) alloys at room temperature. Despite intensive investigation of the electrochemical behaviors of a-Li x Si alloys, their mechanical properties and underlying atomistic mechanisms remain largely unexplored. Here we perform molecular dynamics simulations to characterize the mechanical properties of a-Li x Si with a newly developed reactive force field (ReaxFF). We compute the yield and fracture strengths of a-Li x Si alloys under a variety of chemomechanical loading conditions, including the constrained thin-film lithiation, biaxial compression, uniaxial tension and compression. Effects of loading sequence and stress state are investigated to correlate the mechanical responses with the dominant atomic bonding, featuring a transition from the covalent to the metallic glass characteristics with increasing Li concentration. The results provide mechanistic insights for interpreting experiments, understanding properties and designing new experiments on a-Li x Si alloys, which are essential to the development of durable Si electrodes for high-performance lithium-ion batteries.