Qingliu Wu

Advanced titania nanostructures and composites for lithium ion battery

Owing to the increasing demand of energy and shifting to the renewable energy resources, lithium ion batteries (LIBs) have been considered as the most promising alternative and green technology for energy storage applied in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and other electric utilities. Owing to its environmental benignity, availability, and stable structure, titanium dioxide (TiO2) is one of the most attractive anode materials of LIBs with high capability, long cycling life, high safety, and low cost. However, the poor electrical conductivity and low diffusion coefficient of Li-ions in TiO2 hamper the advancement of TiO2 as anode materials of LIBs. Therefore, intensive research study has been focused on designing the nanostructures of TiO2 and its composites to reduce the diffusion length of Li-ion insertion/extraction and improve the electrical conductivity of the electrode materials. In this article, the development of TiO2 and its composites in nano-scales including fabrication, characterization of TiO2 nanomaterials, TiO2/carbon composite, and TiO2/metal oxide composites to improve their properties (capacity, cycling performance, and energy density) for LIBs are reviewed. Meanwhile, the mechanisms for influences of the structure, surface morphology, and additives to TiO2 composites on the related properties of TiO2 and TiO2 composites to LIBs are discussed. The new directions of research on this field are proposed.

Hierarchically porous titania thin film prepared by controlled phase separation and surfactant templating.

Poly(propylene glycol) (PPG) of moderately high molecular weight (M(n) = 3500 Da) exhibits amphibious behavior in aqueous solution in that it is hydrophilic at low temperature but hydrophobic at high temperature. This property is utilized to generate porous titania thin films with a hierarchical structure consisting of macroporous voids/cracks in films with mesoporous walls. The smaller mesopores result from the self-assembly of the Pluronic block copolymer P123 to form micellar templates in well-ordered arrays with hexagonal symmetry. The larger pores are generated from the phase separation of PPG during aging of the films. The PPG acts to a limited degree as a swelling agent for the P123 micelles, but because the films are aged at a low temperature where PPG is hydrophilic, much of the PPG remains in the polar titania phase. Upon heating, the PPG phase separates to form randomly dispersed, large pores throughout the film while retaining the ordered mesoporous P123-templated structure in the matrix of the material. TEM and SEM imaging confirm that calcined titania thin films have interconnected hierarchical porous structures consisting of ordered mesopores 4-12 nm in diameter and macroporous voids >100 nm in size. The density and size of the voids increase as more PPG is added to the films.

Giant magnetoresistance in non-magnetic phosphoric acid doped polyaniline silicon nanocomposites with higher magnetic field sensing sensitivity

Phosphoric acid doped conductive polyaniline (PANI) polymer nanocomposites (PNCs) reinforced with silicon nanopowders have been successfully synthesized using a facile surface initiated polymerization (SIP) method. The chemical structures of the nanocomposites are characterized using Fourier transform infrared (FT-IR) spectroscopy. The enhanced thermal stability of the silicon-PANI PNCs compared with pure PANI is obtained using thermogravimetric analysis (TGA). The obtained optical band gap of the PNCs using Ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) decreases with increasing silicon loading. The dielectric properties of the PNCs are strongly related to the silicon loading level. Temperature dependent resistivity analysis reveals a quasi 3-D variable range hopping (VRH) electrical conduction mechanism for the synthesized PNCs. Room temperature giant magnetoresistance (GMR) is observed in the synthesized non-magnetic nanocomposites and analyzed using the wave-function shrinkage model.

Effects of oxide additives on sheet resistance of W thick-film conductor

A multilayer AIN-W cofired body has been developed using the pressless sintering technique. Effects of additives, such as Y2O3, CaO, La2O3, MgO, Al2O3 and SiO2, on the sheet resistance of W conductor were studied. The sheet resistance of the W conductor increases with increasing additives in the W paste. However, the oxides can be divided into two groups. The effect of the first group on sheet resistance is different from that of the second group.

Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films

The mesostructure loss kinetics are measured as a function of the orientation of micelles in 2D hexagonal close packed (HCP) columnar mesostructured titania thin films using in situ grazing incidence small angle X-ray scattering (GISAXS). Complementary supporting information is provided by ex situ scanning electron microscopy. Pluronic surfactant P123 acts as the template to synthesize HCP structured titania thin films. When the glass substrates are modified with crosslinked P123, the micelles of the HCP mesophase align orthogonal to the films, whereas a mix of parallel and orthogonal alignment is found on unmodified glass. The rate of mesostructure loss of orthogonally oriented (o-HCP) thin films (∼60 nm thickness) prepared on modified substrate is consistently found to be less by a factor of 2.5 ± 0.35 than that measured for mixed orientation HCP films on unmodified substrates. The activation energy for mesostructure loss is only slightly greater for films on modified glass (155 ± 25 kJ mol(-1)) than on unmodified (128 kJ mol(-1)), which implies that the rate difference stems from a greater activation entropy for mesostructure loss in o-HCP titania films. Nearly perfect orthogonal orientation of micelles on modified surfaces contributes to the lower rate of mesostructure loss by supporting the anisotropic stresses that develop within the films during annealing due to continuous curing, sintering and crystallization into the anatase phase during high temperature calcination (>450 °C). Because the film thickness dictates the propagation of orientation throughout the films and the degree of confinement, thicker (∼250 nm) films cast onto P123-modified substrates have a much lower activation energy for mesostructure loss (89 ± 27 kJ mol(-1)) due to the mix of orientations found in the films. Thus, this kinetic study shows that thin P123-templated o-HCP titania films are not only better able to achieve good orthogonal alignment of the mesophase relative to thicker films or films on unmodified substrates, but that alignment of the mesophase in the films stabilizes the mesophase against thermally-induced mesostructure loss.

Synthesis of Nanoparticles via Solvothermal and Hydrothermal Methods

This chapter summarizes the synthesis of various types of nanoparticles as well as surface modifications of nanomaterials using hydrothermal and solvothermal methods. First, the definition, history, instrumentation, and mechanism of hydrothermal and solvothermal methods as well as the important parameters af-fecting the nucleation and crystal growth of nanomaterials are briefly introduced. Then the specific hydrothermal and solvothermal methods used to grow oxides, Group II-VI, III-V, IV, transitional metals, and metal-organic framework nanoparticles are summarized. Finally, the hydrothermal and solvothermal strategies used for the surface modification of nanomaterials are discussed.

Investigations of Si Thin Films as Anode of Lithium-Ion Batteries

Amorphous silicon thin films having various thicknesses were investigated as a negative electrode material for lithium-ion batteries. Electrochemical characterization of the 20 nm thick thin silicon film revealed a very low first cycle Coulombic efficiency, which can be attributed to the silicon oxide layer formed on both the surface of the as-deposited Si thin film and the interface between the Si and the substrate. Among the investigated films, the 100 nm Si thin film demonstrated the best performance in terms of first cycle efficiency and cycle life. Observations from scanning electron microscopy demonstrated that the generation of cracks was inevitable in the cycled Si thin films, even as the thickness of the film was as little as 20 nm, which was not predicted by previous modeling work. However, the cycling performance of the 20 and 100 nm silicon thin films was not detrimentally affected by these cracks. The poor capacity retention of the 1 μm silicon thin film was attributed to the delamination.