HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Parameter estimation for transformer modeling

Large Power transformers, an aging and vulnerable part of our energy infrastructure, are at choke points in the grid and are key to reliability and security. Damage or destruction due to vandalism, misoperation, or other unexpected events is of great concern, given replacement costs upward of $2M and lead time of 12 months. Transient overvoltages can cause great damage and there is much interest in improving computer simulation models to correctly predict and avoid the consequences. EMTP (the Electromagnetic Transients Program) has been developed for computer simulation of power system transients. Component models for most equipment have been developed and benchmarked. Power transformers would appear to be simple. However, due to their nonlinear and frequency-dependent behaviors, they can be one of the most complex system components to model. It is imperative that the applied models be appropriate for the range of frequencies and excitation levels that the system experiences. Thus, transformer modeling is not a mature field and newer improved models must be made available. In this work, improved topologically-correct duality-based models are developed for three-phase autotransformers having five-legged, three-legged, and shell-form cores. The main problem in the implementation of detailed models is the lack of complete and reliable data, as no international standard suggests how to measure and calculate parameters. Therefore, parameter estimation methods are developed here to determine the parameters of a given model in cases where available information is incomplete. The transformer nameplate data is required and relative physical dimensions of the core are estimated. The models include a separate representation of each segment of the core, including hysteresis of the core, λ-i saturation characteristic, capacitive effects, and frequency dependency of winding resistance and core loss. Steady-state excitation, and de-energization and re-energization transients are simulated and compared with an earlier-developed BCTRAN-based model. Black start energization cases are also simulated as a means of model evaluation and compared with actual event records. The simulated results using the model developed here are reasonable and more correct than those of the BCTRAN-based model. Simulation accuracy is dependent on the accuracy of the equipment model and its parameters. This work is significant in that it advances existing parameter estimation methods in cases where the available data and measurements are incomplete. The accuracy of EMTP simulation for power systems including three-phase autotransformers is thus enhanced. Theoretical results obtained from this work provide a sound foundation for development of transformer parameter estimation methods using engineering optimization. In addition, it should be possible to refine which information and measurement data are necessary for complete duality-based transformer models. To further refine and develop the models and transformer parameter estimation methods developed here, iterative full-scale laboratory tests using high-voltage and high-power three-phase transformer would be helpful.

Advanced Nanostructured Electro-Catalysts for Electricity Generation and Biorenewable Alcohol Conversion

In my Ph.D research, a wet chemistry-based organic solution phase reduction method was developed, and was successfully applied in the preparation of a series of advanced electro-catalysts, including 0-dimensional (0-D) Pt, Pd, Au, and Pd-Ni nanoparticles (NPs), 1-D Pt-Fe nanowires (NWs) and 2-D Pd-Fe nanoleaves (NLs), with controlled size, shape, and morphology. These nanostructured catalysts have demonstrated unique electro-catalytic functions towards electricity production and biorenewable alcohol conversion. The molecular oxygen reduction reaction (ORR) is a long-standing scientific issue for fuel cells due to its sluggish kinetics and the poor catalyst durability. The activity and durability of an electro-catalyst is strongly related with its composition and structure. Based on this point, Pt-Fe NWs with a diameter of 2 - 3 nm were accurately prepared. They have demonstrated a high durability in sulfuric acid due to its 1-D structure, as well as a high ORR activity attributed to its tuned electronic structure. By substituting Pt with Pd using a similar synthesis route, Pd-Fe NLs were prepared and demonstrated a higher ORR activity than Pt and Pd NPs catalysts in the alkaline electrolyte. Recently, biomass-derived alcohols have attracted enormous attention as promising fuels (to replace H2) for low-temperature fuel cells. From this point of view, Pd-Ni NPs were prepared and demonstrated a high electro-catalytic activity towards ethanol oxidation. Comparing to ethanol, the biodiesel waste glycerol is more promising due to its low price and high reactivity. Glycerol (and crude glycerol) was successfully applied as the fuel in an Au-anode anion-exchange membrane fuel cell (AEMFC). By replacing Au with a more active Pt catalyst, simultaneous generation of both high power-density electricity and value-added chemicals (glycerate, tartronate, and mesoxalate) from glycerol was achieved in an AEMFC. To investigate the production of valuable chemicals from glycerol electro-oxidation, two anion-exchange membrane electro-catalytic reactors were designed. The research shows that the electro-oxidation product distribution is strongly dependent on the anode applied potential. Reaction pathways for the electro-oxidation of glycerol on Au/C catalyst have been elucidated: continuous oxidation of OH groups (to produce tartronate and mesoxalate) is predominant at lower potentials, while C-C cleavage (to produce glycolate) is the dominant reaction path at higher potentials.

EXPERIMENTAL INVESTIGATION OF CERTAIN INTERNAL CONDENSING AND BOILING FLOWS: THEIR SENSITIVITY TO PRESSURE FLUCTUATIONS AND HEAT TRANSFER ENHANCEMENTS

Space-based (satellite, scientific probe, space station, etc.) and millimeter – to – microscale (such as are used in high power electronics cooling, weapons cooling in aircraft, etc.) condensers and boilers are shear/pressure driven. They are of increasing interest to system engineers for thermal management because flow boilers and flow condensers offer both high fluid flow-rate-specific heat transfer capacity and very low thermal resistance between the fluid and the heat exchange surface, so large amounts of heat may be removed using reasonably-sized devices without the need for excessive temperature differences. However, flow stability issues and degradation of performance of shear/pressure driven condensers and boilers due to non-desirable flow morphology over large portions of their lengths have mostly prevented their use in these applications. This research is part of an ongoing investigation seeking to close the gap between science and engineering by analyzing two key innovations which could help address these problems. First, it is recommended that the condenser and boiler be operated in an innovative flow configuration which provides a non-participating core vapor stream to stabilize the annular flow regime throughout the device length, accomplished in an energy-efficient manner by means of ducted vapor re-circulation. This is demonstrated experimentally. Second, suitable pulsations applied to the vapor entering the condenser or boiler (from the re-circulating vapor stream) greatly reduce the thermal resistance of the already effective annular flow regime. For experiments reported here, application of pulsations increased time-averaged heat-flux up to 900 % at a location within the flow condenser and up to 200 % at a location within the flow boiler, measured at the heat-exchange surface. Traditional fully condensing flows, reported here for comparison purposes, show similar heat-flux enhancements due to imposed pulsations over a range of frequencies. Shear/pressure driven condensing and boiling flow experiments are carried out in horizontal mm-scale channels with heat exchange through the bottom surface. The sides and top of the flow channel are insulated. The fluid is FC-72 from 3M Corporation.

Translation Studies on an Annular Field Reversed Configuration Device for Space Propulsion

This research investigated annular field reversed configuration (AFRC)devices for high power electric propulsion by demonstrating the acceleration of these plasmoids using an experimental prototype and measuring the plasmoid's velocity, impulse, and energy efficiency. The AFRC plasmoid translation experiment was design and constructed with the aid of a dynamic circuit model. Two versions of the experiment were built, using underdamped RLC circuits at 10 kHz and 20 kHz. Input energies were varied from 100 J/pulse to 1000 J/pulse for the 10 kHz bank and 100 J/pulse for the 20 kHz bank. The plasmoids were formed in static gas fill of argon, from 1 mTorr to 50 mTorr. The translation of the plasmoid was accomplished by incorporating a small taper into the outer coil, with a half angle of 2°. Magnetic field diagnostics, plasma probes, and single-frame imaging were used to measure the plasmoid's velocity and to diagnose plasmoid behavior. Full details of the device design, construction, and diagnostics are provided in this dissertation. The results from the experiment demonstrated that a repeatable AFRC plasmoid was produced between the coils, yet failed to translate for all tested conditions. The data revealed the plasmoid was limited in lifetime to only a few (4-10) μs, too short for translation at low energy. A global stability study showed that the plasma suffered a radial collapse onto the inner wall early in its lifecycle. The radial collapse was traced to a magnetic pressure imbalance. A correction made to the circuit was successful in restoring an equilibrium pressure balance and prolonging radial stability by an additional 2.5 μs. The equilibrium state was sufficient to confirm that the plasmoid current in an AFRC reaches a steady-state prior to the peak of the coil currents. This implies that the plasmoid will always be driven to the inner wall, unless it translates from the coils prior to peak coil currents. However, ejection of the plasmoid before the peak coil currents results in severe efficiency losses. These results demonstrate the difficulty in designing an AFRC experiment for translation as balancing the different requirements for stability, balance, and efficient translation can have competing consequences.

Design of high fidelity building energy monitoring system

Building energy meter network, based on per-appliance monitoring system, willbe an important part of the Advanced Metering Infrastructure. Two key issues exist for designing such networks. One is the network structure to be used. The other is the implementation of the network structure on a large amount of small low power devices, and the maintenance of high quality communication when the devices have electric connection with high voltage AC line. The recent advancement of low-power wireless communication makes itself the right candidate for house and building energy network. Among all kinds of wireless solutions, the low speed but highly reliable 802.15.4 radio has been chosen in this design. While many network-layer solutions have been provided on top of 802.15.4, an IPv6 based method is used in this design. 6LOWPAN is the particular protocol which adapts IP on low power personal network radio. In order to extend the network into building area without, a specific network layer routing mechanism-RPL, is included in this design. The fundamental unit of the building energy monitoring system is a smart wall plug. It is consisted of an electricity energy meter, a RF communication module and a low power CPU. The real challenge for designing such a device is its network firmware. In this design, IPv6 is implemented through Contiki operation system. Customize hardware driver and meter application program have been developed on top of the Contiki OS. Some experiments have been done, in order to prove the network ability of this system.