To utilize high-capacity Si anodes in next-generation Li-ion batteries, the physical and chemical transformations during the Li-Si reaction must be better understood. Here, in situ transmission electron microscopy is used to observe the lithiation/delithiation of amorphous Si nanospheres; amorphous Si is an important anode material that has been less studied than crystalline Si. Unexpectedly, the experiments reveal that the first lithiation occurs via a two-phase mechanism, which is contrary to previous understanding and has important consequences for mechanical stress evolution during lithiation. On the basis of kinetics measurements, this behavior is suggested to be due to the rate-limiting effect of Si-Si bond breaking. In addition, the results show that amorphous Si has more favorable kinetics and fracture behavior when reacting with Li than does crystalline Si, making it advantageous to use in battery electrodes. Amorphous spheres up to 870 nm in diameter do not fracture upon lithiation; this is much larger than the 150 nm critical fracture diameter previously identified for crystalline Si spheres.

A nonwoven fabric with paperlike qualities composed of silicon nanowires is reported. The nanowires, made by the supercritical-fluid-liquid-solid process, are crystalline, range in diameter from 10 to 50 nm with an average length of >100 μm, and are coated with a thin chemisorbed polyphenylsilane shell. About 90% of the nanowire fabric volume is void space. Thermal annealing of the nanowire fabric in a reducing environment converts the polyphenylsilane coating to a carbonaceous layer that significantly increases the electrical conductivity of the material. This makes the nanowire fabric useful as a self-supporting, mechanically flexible, high-energy-storage anode material in a lithium ion battery. Anode capacities of more than 800 mA h g(-1) were achieved without the addition of conductive carbon or binder.

It is generally accepted that the magnetic component of light has a minor role in the lightmatter interaction. The recent discovery of metamaterials has broken this traditional understanding, as both the electric and the magnetic field are key ingredients in metamaterials. The top-down technology used so far employs noble metals with large intrinsic losses. Here we report on a bottom-up approach for processing metamaterials based on suspensions of monodisperse full dielectric silicon nanocavities with a large magnetic response in the near-infrared region. Experimental results and theory show that siliconcolloid-based liquid suspensions and photonic crystals made of two-dimensional arrays of particles have strong magnetic response in the near-infrared region with small optical losses. Our findings might have important implications in the bottom-up processing of large-area low-loss metamaterials working in the near-infrared region.

Both silicon and germanium are leading candidates to replace the carbon anode of lithium ions batteries. Silicon is attractive because of its high lithium storage capacity while germanium, a superior electronic and ionic conductor, can support much higher charge/discharge rates. Here we investigate the electronic, electrochemical and optical properties of Si(1-x)Gex thin films with x = 0, 0.25, 0.5, 0.75, and 1. Glancing angle deposition provided amorphous films of reproducible nanostructure and porosity. The film's composition and physical properties were investigated by X-ray photoelectron spectroscopy, four-point probe conductivity, Raman, and UV-vis absorption spectroscopy. The films were assembled into coin cells to test their electrochemical properties as a lithium-ion battery anode material. The cells were cycled at various C-rates to determine the upper limits for high rate performance. Adjusting the composition in the Si(1-x)Gex system demonstrates a trade-off between rate capability and specific capacity. We show that high-capacity silicon anodes and high-rate germanium anodes are merely the two extremes; the composition of Si(1-x)Gex alloys provides a new parameter to use in electrode optimization.

Colloidally grown hydrogenated amorphous silicon (a-Si:H) particles offer promise as anodes for lithium ion batteries with a much higher energy density than graphite. We have found that significantly improved battery cycle performance and enhanced lithium storage capacity (by a factor of 7) is achieved by depositing copper (Cu) on the a-Si:H particles using a polyol reduction method. The superior performance appears to result from an electronically conducting network formed by the Cu coating. High-resolution interfacial spectroelectrochemical studies with in situ Raman spectroscopy illustrates the role of Cu coating over a-Si:H particles and provides insight into improving low Coulombic efficiency and capacity fading on cycling of Si-based anodes in Li-ion batteries.

Pyrite-phase iron sulfide (FeS2) nanocrystals were synthesized to form solvent-based dispersions, or "solar paint," to fabricate photovoltaic devices (PVs). Nanocrystals were sprayed onto substrates as absorber layers in devices with several different architectures, including Schottky barrier, heterojunction, and organic/inorganic hybrid architectures, to explore their viability as a PV material. None of the devices exhibited PV response. XRD and Raman spectroscopy confirmed the pyrite composition and phase purity of the nanocrystals. The electrical conductivity of the nanocrystal films was about 4 to 5 S/cm, more typical of metal nanocrystal films than semiconductor nanocrystal films, and the lack of PV response appears to derive from the highly conductive surface-related defects in pyrite that have been proposed.

Colloidal particles of hydrogenated amorphous silicon (a-Si:H) were synthesized by decomposition of trisilane (Si 3 H 8 ) in supercritical n-hexane (sc-hexane) at temperatures ranging from 380 to 550 °C. The reaction temperature, pressure and Si 3 H 8 concentration have a significant influence on the average particle size, Si bond order and hydrogen content. The particle diameter could be varied from 170 nm to 1.7 μm, with hydrogen loadings between 10% and 58%. Raman spectroscopy of the particles revealed significant differences in Si bond order that correlated with hydrogen content, with the lowest reaction temperatures yielding particles with the least structural order and most associated hydrogen. Particles synthesized at temperatures higher than 420 °C had sufficient bond order to allow crystallization under the Raman laser probe.

Binder-free graphene-supported Ge nanowires, Si nanowires, and Si nanocrystals were studied for use as negative electrode materials in rechargeable lithium ion batteries (LIBs). Graphene obtained from reduced graphene oxide (RGO) helped stabilize electrochemical cycling of all of the nanomaterials. However, differential capacity plots revealed competition between RGO and Si/Ge lithiation. At high Si/Ge loading (>50% w/w) and low cycle rates (C/10), RGO lithiation begins to dominate. Under those conditions, only Ge nanowires exhibited significant lithiation relative to RGO, most likely due to the inherently faster lithiation of Ge compared to Si.