Toward silicon anodes for next-generation lithium ion batteries: a comparative performance study of various polymer binders and silicon nanopowders.

Silicon is widely regarded as one of the most promising anode materials for lithium ion and next-generation lithium batteries because of its high theoretical specific capacity. However, major issues arise from the large volume changes during alloying with lithium. In recent years, much effort has been spent on preparing nanostructured silicon and optimizing various aspects of material processing with the goal of preserving the electrode integrity upon lithiation/delithiation. The performance of silicon anodes is known to depend on a large number of parameters and, thus, the general definition of a "standard" is virtually impossible. In this work, we conduct a comparative performance study of silicon anode tapes prepared from commercially available materials while using both a well-defined electrode configuration and cycling method. Our results demonstrate that the polymer binder has a profound effect on the cell performance. Furthermore, we show that key parameters such as specific capacity, capacity retention, rate capability, and so forth can be strongly affected by the choice of silicon material, polymer binder and electrolyte system - even the formation of metastable crystalline Li15Si4 is found to depend on the electrode composition and low potential exposure time. Overall, the use of either poly(acrylic acid) with a viscosity-average molecular weight of 450.000 or poly(vinyl alcohol) Selvol 425 in combination with both silicon nanopowder containing a native oxide surface layer of ∼1 nm in diameter and with a monofluoroethylene carbonate-based electrolyte led to improved cycling stability at high loadings.

Low-temperature formation of cubic ß-PbF2: precursor-based synthesis and first-principles phase stability study.

A precursor-based approach to the cubic ß-phase of PbF(2) was developed and allowed the preparation of this high-temperature phase well below the temperature for transition from the orthorhombic α- to the cubic ß-phase. The formation of ß-PbF(2) from the molecular precursors Pb[Se(C(6)H(2)(CF(3))(3))](2) and Pb(C(6)H(2)(CF(3))(3))(2) is facilitated by the presence of several short PbF contacts in these molecules. The cubic form of PbF(2) was obtained as macroscopic crystals as well as nanoparticulate powder. Its formation at relatively low temperature suggested a theoretical re-investigation of the phase stabilities of the two polymorphs. The theoretical results from the Kohn-Sham density functional theory indicate that the energy content for the ß-phase is slightly lower than the one for the α-phase, by 0.5-1.7 kJ mol(-1) depending on the density functional used (zero-point vibrational energy correction included).

Polymer-assisted preparation of nanoscale films of thermoelectric PbSe and PbTe and of lead chalcogenide-polymer composite films.

Polymer films of polyethyleneoxide (PEO) or poly(L-lactide) (PLLA) containing a single-source precursor for either PbSe or PbTe were used to produce films of nanoparticles of these thermoelectric materials. The monomeric homoleptic chalcogenolates lead(II) bis-(2,4,6-trifluoromethylphenylselenolate) Pb[SeC(6)H(2)(CF(3))(3)](2) and lead(II) bis-[tris(trimethylsilyl)silyl-tellurolate] Pb[TeSi(SiMe(3))(3)](2) were used as single-source precursors for the thermolytic formation of the lead chalcogenides. The thickness and the quality of as-obtained thin films depended decisively on the spin-coating conditions, on the polymer, on the precursor concentration in the composite film before thermolysis and on the annealing time. Thin layers of particles of 30-50 nm size and high crystallinity were obtained. They were characterized by X-ray diffraction, thermal analysis and electron microscopy.

Thin-walled Er3+:Y2O3 nanotubes showing up-converted fluorescence.

Up-converted red and green fluorescence has been measured in low-crystallinity Er3+:Y2O3 nanotubes upon IR excitation. A new preparation procedure for thin-walled erbium doped yttria nanotubes using alumina templates as shape defining tools and rare earth nitrates as precursors for a purely thermolytic production of erbium doped yttria was developed. The products with a diameter of approximately 40-50 nm and a wall thickness of only 6-8 nm showed up-converted fluorescence with green and red emission bands when excited at 815 nm. The fluorescence properties are compared to the ones of bulk erbium-doped yttria obtained from the same precursor system.

Nanoscale zinc antimonides: synthesis and phase stability.

Highly crystalline single-phase nanoparticles of the important thermoelectric materials Zn4Sb3 and ZnSb were prepared from solvochemically activated powders of elemental zinc and elemental antimony. Low-temperature reactions with reaction temperatures of 275-300 degrees C were applied using an excess of elemental zinc. The nanoscale thermoelectrics obtained were characterized by X-ray powder diffraction, transmission electron microscopy, and thermal analysis. nc-Zn4Sb3 showed particle sizes of 50-70 nm, whereas particle sizes of 15-20 nm were observed for nc-ZnSb. Calorimetric investigations showed an increased heat capacity, Cp, for nc-Zn4Sb3 with respect to the bulk material which could be reduced to the bulk value by annealing nc-Zn4Sb3 at 190 degrees C. Interestingly, nc-Zn4Sb3 showed exothermic decomposition into zinc-poorer ZnSn at 196 degrees C in an open system, indicating that Zn4Sb3 is metastable in nanocrystalline form at room temperature.