NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

CHARACTERIZATION OF THE ATMOSPHERIC EFFECTS ON THE TRANSMISSION OF THERMAL RADIATION

Atmospheric scattering plays a crucial rule in degrading the performance of electro optical imaging systems operating in the visible and infra-red spectral bands, and hence limits the quality of the acquired images, either through reduction of contrast or increase of image blur. The exact nature of light scattering by atmospheric media is highly complex and depends on the types, orientations, sizes and distributions of particles constituting these media, as well as wavelengths, polarization states and directions of the propagating radiation. Here we follow the common approach for solving imaging and propagation problems by treating the propagating light through atmospheric media as composed of two main components: a direct (unscattered), and a scattered component. In this work we developed a detailed model of the effects of absorption and scattering by haze and fog atmospheric aerosols on the optical radiation propagating from the object plane to an imaging system, based on the classical theory of EM scattering. This detailed model is then used to compute the average point spread function (PSF) of an imaging system which properly accounts for the effects of the diffraction, scattering, and the appropriate optical power level of both the direct and the scattered radiation arriving at the pupil of the imaging system. Also, the calculated PSF, properly weighted for the energy contributions of the direct and scattered components is used, in combination with a radiometric model, to estimate the average number of the direct and scattered photons detected at the sensor plane, which are then used to calculate the image spectrum signal to- noise ratio (SNR) in the visible near infra-red (NIR) and mid infra-red (MIR) spectral wavelength bands. Reconstruction of images degraded by atmospheric scattering and measurement noise is then performed, up to the limit imposed by the noise effective cutoff spatial frequency of the image spectrum SNR. Key results of this research are as follows: A mathematical model based on Mie scattering theory for how scattering from aerosols affects the overall point spread function (PSF) of an imaging system was developed, coded in MATLAB, and demonstrated. This model along with radiometric theory was used to predict the limiting resolution of an imaging system as a function of the optics, scattering environment, and measurement noise. Finally, image reconstruction algorithms were developed and demonstrated which mitigate the effects of scattering-induced blurring to within the limits imposed by noise.