Low-Temperature Molten-Salt Production of Silicon Nanowires by the Electrochemical Reduction of CaSiO3.

Silicon is an extremely important technological material, but its current industrial production by the carbothermic reduction of SiO2 is energy intensive and generates CO2 emissions. Herein, we developed a more sustainable method to produce silicon nanowires (Si NWs) in bulk quantities through the direct electrochemical reduction of CaSiO3 , an abundant and inexpensive Si source soluble in molten salts, at a low temperature of 650 °C by using low-melting-point ternary molten salts CaCl2 -MgCl2 -NaCl, which still retains high CaSiO3 solubility, and a supporting electrolyte of CaO, which facilitates the transport of O2- anions, drastically improves the reaction kinetics, and enables the electrolysis at low temperatures. The Si nanowire product can be used as high-capacity Li-ion battery anode materials with excellent cycling performance. This environmentally friendly strategy for the practical production of Si at lower temperatures can be applied to other molten salt systems and is also promising for waste glass and coal ash recycling.

High performance Na-doped PbTe-PbS thermoelectric materials: electronic density of states modification and shape-controlled nanostructures.

Thermoelectric heat-to-power generation is an attractive option for robust and environmentally friendly renewable energy production. Historically, the performance of thermoelectric materials has been limited by low efficiencies, related to the thermoelectric figure-of-merit ZT. Nanostructuring thermoelectric materials have shown to enhance ZT primarily via increasing phonon scattering, beneficially reducing lattice thermal conductivity. Conversely, density-of-states (DOS) engineering has also enhanced electronic transport properties. However, successfully joining the two approaches has proved elusive. Herein, we report a thermoelectric materials system whereby we can control both nanostructure formations to effectively reduce thermal conductivity, while concurrently modifying the electronic structure to significantly enhance thermoelectric power factor. We report that the thermoelectric system PbTe-PbS 12% doped with 2% Na produces shape-controlled cubic PbS nanostructures, which help reduce lattice thermal conductivity, while altering the solubility of PbS within the PbTe matrix beneficially modifies the DOS that allow for enhancements in thermoelectric power factor. These concomitant and synergistic effects result in a maximum ZT for 2% Na-doped PbTe-PbS 12% of 1.8 at 800 K.

In situ nanostructure generation and evolution within a bulk thermoelectric material to reduce lattice thermal conductivity.

We show experimentally the direct reduction in lattice thermal conductivity as a result of in situ nanostructure generation within a thermoelectric material. Solid solution alloys of the high-performance thermoelectric PbTe-PbS 8% can be synthesized through rapid cooling and subsequent high-temperature activation that induces a spontaneous nucleation and growth of PbS nanocrystals. The emergence of coherent PbS nanostructures reduces the lattice thermal conductivity from approximately 1 to approximately 0.4 W/mK between 400 and 500 K.

On the origin of increased phonon scattering in nanostructured PbTe based thermoelectric materials.

We have investigated the possible mechanisms of phonon scattering by nanostructures and defects in PbTe-X (X = 2% Sb, Bi, or Pb) thermoelectric materials systems. We find that among these three compositions, PbTe-2% Sb has the lowest lattice thermal conductivity and exhibits a larger strain and notably more misfit dislocations at the precipitate/PbTe interfaces than the other two compositions. In the PbTe-Bi 2% sample, we infer some weaker phonon scattering BiTe precipitates, in addition to the abundant Bi nanostructures. In the PbTe-Pb 2% sample, we also find that pure Pb nanoparticles exhibit stronger phonon scattering than nanostructures with Te vacancies. Within the accepted error range, the theoretical calculations of the lattice thermal conductivity in the three systems are in close agreement with the experimental measurements, highlighting the important role of misfit dislocations, nanoscale particles, and associated interfacial elastic strain play in phonon scattering. We further propose that such particle-induced local elastic perturbations interfere with the phonon propagation pathway, thereby contributing to further reduction in lattice thermal conductivity, and consequently can enhance the overall thermoelectric figure of merit.

Twisting phonons in complex crystals with quasi-one-dimensional substructures.

A variety of crystals contain quasi-one-dimensional substructures, which yield distinctive electronic, spintronic, optical and thermoelectric properties. There is a lack of understanding of the lattice dynamics that influences the properties of such complex crystals. Here we employ inelastic neutron scatting measurements and density functional theory calculations to show that numerous low-energy optical vibrational modes exist in higher manganese silicides, an example of such crystals. These optical modes, including unusually low-frequency twisting motions of the Si ladders inside the Mn chimneys, provide a large phase space for scattering acoustic phonons. A hybrid phonon and diffuson model is proposed to explain the low and anisotropic thermal conductivity of higher manganese silicides and to evaluate nanostructuring as an approach to further suppress the thermal conductivity and enhance the thermoelectric energy conversion efficiency. This discovery offers new insights into the structure-property relationships of a broad class of materials with quasi-one-dimensional substructures for various applications.

High-purity iron pyrite (FeS2) nanowires as high-capacity nanostructured cathodes for lithium-ion batteries.

Iron pyrite is an earth-abundant and inexpensive material that has long been interesting for electrochemical energy storage and solar energy conversion. A large-scale conversion synthesis of phase-pure pyrite nanowires has been developed for the first time. Nano-pyrite cathodes exhibited high Li-storage capacity and excellent capacity retention in Li/pyrite batteries using a liquid electrolyte, which retained a discharge capacity of 350 mAh g(-1) and a discharge energy density of 534 Wh kg(-1) after 50 cycles at 0.1 C rate.

Facile and scalable synthesis of Ti5Si3 nanoparticles in molten salts for metal-matrix nanocomposites.

We report a novel synthesis of Ti5Si3 nanoparticles (NPs) via the magnesio-reduction of TiO2 NPs and SiO2 in eutectic LiCl-KCl molten salts at 700 °C. The Ti5Si3 particle size (∼25 nm) is confined to the nanoscale due to the partial dissolution of Mg and silica in the molten salts and a subsequent heterogeneous reduction on the surface of the TiO2 NPs.

Strong phonon scattering by layer structured PbSnS(2) in PbTe based thermoelectric materials.

The incorporation of PbSnS(2) in PbTe results in a tremendous reduction of the lattice thermal conductivity to 0.8 W/mK at room temperature, a reduction of almost 60% over bulk PbTe. Transmission electron microscopy reveals very high density displacement layers, misfit dislocations, and phase boundaries. Our thermal transport calculations based on modified Debye-Callaway model, well in agreement with the experimental measurements, reveal that the layer structured PbSnS(2) plays an important role in reducing the lattice thermal conductivity.