Microwave-assisted wet chemical (MAWC) synthesis of lithium iron phosphate

LiFePO4 is a Co-free battery material. Its advantages of low cost, non-toxic and flat discharge plateau show promising for vehicle propulsion applications. A major problem associated with this material is its low electrical conductivity. Use of nanosized LiFePO4 coated with carbon is considered a solution because the nanosized particles have much shorter path for L+ ions to travel from the LiFePO4 crystal lattice to electrolytes. As other nano material powders, however, nano LiFePO4 could have processing and health issues. In order to achieve high electrical conductivity while maintaining a satisfactory manufacturability, the particles should possess both of the nano- and the microcharacteristics correspondingly. These two contradictory requirements could only be fulfilled if the LiFePO4 powders have a hierarchical structure: micron-sized parent particles assembled by nanosized crystallites with appropriate electrolyte communication channels. This study addressed the issue by study of the formation and development mechanisms of the LiFePO4 crystallites and their microstructures. Microwaveassisted wet chemical (MAWC) synthesis approach was employed in order to facilitate the evolvement of the nanostructures. The results reveal that the LiFePO4 crystallites were directly nucleated from amorphous precursors by competition against other low temperature phases, Li3PO4 and Fe3(PO4)2•8H2O. Growth of the crystalline LiFePO4 particles went through oriented attachment first, followed by revised Ostwald ripening and then recrystallization. While recrystallization played the role in growth of well crystallized particles, oriented attachment and revised Ostwald ripening were responsible for formation of the straight edge and plate-like shaped LiFePO4 particles comprised of nanoscale substructure. Oriented attachment and revised Ostwald ripening seemed to be also responsible for clustering the plate-like LiFePO4 particles into a high-level aggregated structure. The finding from this study indicates a hope for obtaining the hierarchical structure of LiFePO4 particles that could exhibit the both micro- and nano- scale characteristics. Future study is proposed to further advance the understanding of the structural development mechanisms, so that they can be manipulated for new LiFePO4 structures ideal for battery application.

Multi-node TOA-DOA cooperative LOS-NLOS localization : enabling high accuracy and reliability

This dissertation investigates high performance cooperative localization in wireless environments based on multi-node time-of-arrival (TOA) and direction-of-arrival (DOA) estimations in line-of-sight (LOS) and non-LOS (NLOS) scenarios. Here, two categories of nodes are assumed: base nodes (BNs) and target nodes (TNs). BNs are equipped with antenna arrays and capable of estimating TOA (range) and DOA (angle). TNs are equipped with Omni-directional antennas and communicate with BNs to allow BNs to localize TNs; thus, the proposed localization is maintained by BNs and TNs cooperation. First, a LOS localization method is proposed, which is based on semi-distributed multi-node TOA-DOA fusion. The proposed technique is applicable to mobile ad-hoc networks (MANETs). We assume LOS is available between BNs and TNs. One BN is selected as the reference BN, and other nodes are localized in the coordinates of the reference BN. Each BN can localize TNs located in its coverage area independently. In addition, a TN might be localized by multiple BNs. High performance localization is attainable via multi-node TOA-DOA fusion. The complexity of the semi-distributed multi-node TOA-DOA fusion is low because the total computational load is distributed across all BNs. To evaluate the localization accuracy of the proposed method, we compare the proposed method with global positioning system (GPS) aided TOA (DOA) fusion, which are applicable to MANETs. The comparison criterion is the localization circular error probability (CEP). The results confirm that the proposed method is suitable for moderate scale MANETs, while GPS-aided TOA fusion is suitable for large scale MANETs. Usually, TOA and DOA of TNs are periodically estimated by BNs. Thus, Kalman filter (KF) is integrated with multi-node TOA-DOA fusion to further improve its performance. The integration of KF and multi-node TOA-DOA fusion is compared with extended-KF (EKF) when it is applied to multiple TOA-DOA estimations made by multiple BNs. The comparison depicts that it is stable (no divergence takes place) and its accuracy is slightly lower than that of the EKF, if the EKF converges. However, the EKF may diverge while the integration of KF and multi-node TOA-DOA fusion does not; thus, the reliability of the proposed method is higher. In addition, the computational complexity of the integration of KF and multi-node TOA-DOA fusion is much lower than that of EKF. In wireless environments, LOS might be obstructed. This degrades the localization reliability. Antenna arrays installed at each BN is incorporated to allow each BN to identify NLOS scenarios independently. Here, a single BN measures the phase difference across two antenna elements using a synchronized bi-receiver system, and maps it into wireless channel’s K-factor. The larger K is, the more likely the channel would be a LOS one. Next, the K-factor is incorporated to identify NLOS scenarios. The performance of this system is characterized in terms of probability of LOS and NLOS identification. The latency of the method is small. Finally, a multi-node NLOS identification and localization method is proposed to improve localization reliability. In this case, multiple BNs engage in the process of NLOS identification, shared reflectors determination and localization, and NLOS TN localization. In NLOS scenarios, when there are three or more shared reflectors, those reflectors are localized via DOA fusion, and then a TN is localized via TOA fusion based on the localization of shared reflectors.

Experimental investigation of regular fluids and nanofluids during flow boiling in a single microchannel at different heat fluxes and mass fluxes

The dissipation of high heat flux from integrated circuit chips and the maintenance of acceptable junction temperatures in high powered electronics require advanced cooling technologies. One such technology is two-phase cooling in microchannels under confined flow boiling conditions. In macroscale flow boiling bubbles will nucleate on the channel walls, grow, and depart from the surface. In microscale flow boiling bubbles can fill the channel diameter before the liquid drag force has a chance to sweep them off the channel wall. As a confined bubble elongates in a microchannel, it traps thin liquid films between the heated wall and the vapor core that are subject to large temperature gradients. The thin films evaporate rapidly, sometimes faster than the incoming mass flux can replenish bulk fluid in the microchannel. When the local vapor pressure spike exceeds the inlet pressure, it forces the upstream interface to travel back into the inlet plenum and create flow boiling instabilities. Flow boiling instabilities reduce the temperature at which critical heat flux occurs and create channel dryout. Dryout causes high surface temperatures that can destroy the electronic circuits that use two-phase micro heat exchangers for cooling. Flow boiling instability is characterized by periodic oscillation of flow regimes which induce oscillations in fluid temperature, wall temperatures, pressure drop, and mass flux. When nanofluids are used in flow boiling, the nanoparticles become deposited on the heated surface and change its thermal conductivity, roughness, capillarity, wettability, and nucleation site density. It also affects heat transfer by changing bubble departure diameter, bubble departure frequency, and the evaporation of the micro and macrolayer beneath the growing bubbles. Flow boiling was investigated in this study using degassed, deionized water, and 0.001 vol% aluminum oxide nanofluids in a single rectangular brass microchannel with a hydraulic diameter of 229 µm for one inlet fluid temperature of 63°C and two constant flow rates of 0.41 ml/min and 0.82 ml/min. The power input was adjusted for two average surface temperatures of 103°C and 119°C at each flow rate. High speed images were taken periodically for water and nanofluid flow boiling after durations of 25, 75, and 125 minutes from the start of flow. The change in regime timing revealed the effect of nanoparticle suspension and deposition on the Onset of Nucelate Boiling (ONB) and the Onset of Bubble Elongation (OBE). Cycle duration and bubble frequencies are reported for different nanofluid flow boiling durations. The addition of nanoparticles was found to stabilize bubble nucleation and growth and limit the recession rate of the upstream and downstream interfaces, mitigating the spreading of dry spots and elongating the thin film regions to increase thin film evaporation.