Lithium silicide (LixSi) is the lithiated form of silicon, one of the most promising anode materials for the next generation of lithium-ion batteries (LIBs). In contrast to silicon, LixSi has not been well studied. Herein we report a facile high-energy ball-milling-based synthesis of four phase-pure LixSi (x = 4.4, 3.75, 3.25, and 2.33), using hexane as the lubricant. Surprisingly, the obtained Li3.75Si phase shows significant downward shifts in all X-ray diffraction peak positions, compared with the standard. Our interpretation is that the high-energy ball-mill-synthesized Li3.75Si presents smaller internal pressures and larger lattice constants. The chemical-stability study reveals that only surface reactions occur after Li4.4Si and Li3.75Si are immersed in several battery-assembly-related chemicals. The thermal-stability study shows that Li4.4Si is stable up to 350 °C and Li3.75Si is stable up to 200 °C. This remarkable thermal stability of Li3.75Si is in stark contrast to the long-observed metastability for electrochemically synthesized Li3.75Si. The carbon encapsulation of Li4.4Si has also been studied for its potential applications in LIBs.
A simple and generic approach--alternating voltage induced electrochemical synthesis (AVIES)--has been reported for synthesizing highly dispersed colloidal metal (Au, Pt, Sn, and Pt-Pd) and metal oxide (ZnO and TiO2) nanocrystals. The respective nanocrystals are produced when a zero-offset alternating voltage at 60 Hz is applied to a pair of identical metal wires, which are inserted in an electrolyte solution containing capping ligands. In the case of Au, the obtained nanocrystals are highly crystalline nano-icosahedra of 14 ± 2 nm in diameter, the smallest Au icosahedra synthesized in aqueous solutions via green chemistry. Their catalytic activity has been demonstrated through facilitating the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride. This AVIES approach is an environmentally benign process and can be adopted by any research lab.
Colloidal iron pyrite nanocrystals (or FeS 2 NC inks) are desirable as active materials in lithium ion batteries and photovoltaics and are particularly suitable for large-scale, roll-to-roll deposition or inkjet printing. However, to date, FeS 2 NC inks have only been synthesized using the hot-injection technique, which requires air-free conditions and may not be desirable at an industrial scale. Here, we report the synthesis of monodisperse, colloidal, spherical, and phase-pure FeS 2 NCs of 5.5 ± 0.3 nm in diameter via a scalable solvothermal method using iron diethyldithiocarbamate as the precursor, combined with a postdigestive ripening process. The phase purity and crystallinity are determined using X-ray diffraction, transmission electron microscopy, farinfrared spectroscopy, and Raman spectroscopy techniques. Through this study, a hypothesis has been verified that solvothermal syntheses can also produce FeS 2 NC inks by incorporating three experimental conditions: high solubility of the precursor, efficient mass transport, and sufficient stabilizing ligands. The addition of ligands and stirring decrease the NC size and led to a narrow size distribution. Moreover, using density functional theory calculations, we have identified an acid-mediated decomposition of the precursor as the initial and critical step in the synthesis of FeS 2 from iron diethyldithiocarbamate.
The synthesis of colloidal nanocrystals (NCs) of lithiated group 14 elements (Z=Si, Ge, and Sn) is reported, which are Li4.4 Si, Li3.75 Si, Li4.4 Ge, and Li4.4 Sn. Lix Z compounds are highly reactive and cannot be synthesized by existing methods. The success relied on separating the surface protection from the crystal formation and using a unique passivating ligand. Bare Lix Z crystals were first produced by milling elemental Li and Z in an argon-filled jar. Then, under the assistance of additional milling, hexyllithium was added to passivate the freshly generated Lix Z NCs. This ball-milling-assisted surface protection method may be generalized to similar systems, such as Nax Z and Kx Z. Moreover, Li4.4 Si and Li4.4 Ge NCs were conformally encapsulated in carbon fibers, providing great opportunities for studying the potential of using Lix Z to mitigate the volume-fluctuation-induced poor cyclability problem confronted by Z anodes in lithium-ion batteries.
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