EVALUATION OF MAGNESIUM AS A HALL THRUSTER PROPELLANT

In this study, the use of magnesium as a Hall thruster propellant was evaluated. A xenon Hall thruster was modified such that magnesium propellant could be loaded into the anode and use waste heat from the thruster discharge to drive the propellant vaporization. A control scheme was developed, which allowed for precise control of the mass flow rate while still using plasma heating as the main mechanism for evaporation. The thruster anode, which also served as the propellant reservoir, was designed such that the open area was too low for sufficient vapor flow at normal operating temperatures (i.e. plasma heating alone). The remaining heat needed to achieve enough vapor flow to sustain thruster discharge came from a counter-wound resistive heater located behind the anode. The control system has the ability to arrest thermal runaway in a direct evaporation feed system and stabilize the discharge current during voltage-limited operation. A proportional-integral-derivative control algorithm was implemented to enable automated operation of the mass flow control system using the discharge current as the measured variable and the anode heater current as the controlled parameter. Steady-state operation at constant voltage with discharge current excursions less than 0.35 A was demonstrated for 70 min. Using this long-duration method, stable operation was achieved with heater powers as low as 6% of the total discharge power. Using the thermal mass flow control system the thruster operated stably enough and long enough that performance measurements could be obtained and compared to the performance of the thruster using xenon propellant. It was found that when operated with magnesium, the thruster has thrust ranging from 34 mN at 200 V to 39 mN at 300 V with 1.7 mg/s of propellant. It was found to have 27 mN of thrust at 300 V using 1.0 mg/s of propellant. The thrust-to-power ratio ranged from 24 mN/kW at 200 V to 18 mN/kW at 300 volts. The specific impulse was 2000 s at 200 V and upwards of 2700 s at 300 V. The anode efficiency was found to be ~23% using magnesium, which is substantially lower than the 40% anode efficiency of xenon at approximately equivalent molar flow rates. Measurements in the plasma plume of the thruster—operated using magnesium and xenon propellants—were obtained using a Faraday probe to measure off-axis current distribution, a retarding potential analyzer to measure ion energy, and a double Langmuir probe to measure plasma density, electron temperature, and plasma potential. Additionally, the off axis current distributions and ion energy distributions were compared to measurements made in krypton and bismuth plasmas obtained in previous studies of the same thruster. Comparisons showed that magnesium had the largest beam divergence of the four propellants while the others had similar divergence. The comparisons also showed that magnesium and krypton both had very low voltage utilization compared to xenon and bismuth. It is likely that the differences in plume structure are due to the atomic differences between the propellants; the ionization mean free path goes down with increasing atomic mass. Magnesium and krypton have long ionization mean free paths and therefore require physically larger thruster dimensions for efficient thruster operation and would benefit from magnetic shielding.

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.

Water transport in complex, non-wetting porous layers with applications to water management in low temperature fuel cells

An experimental setup was designed to visualize water percolation inside the porous transport layer, PTL, of proton exchange membrane, PEM, fuel cells and identify the relevant characterization parameters. In parallel with the observation of the water movement, the injection pressure (pressure required to transport water through the PTL) was measured. A new scaling for the drainage in porous media has been proposed based on the ratio between the input and the dissipated energies during percolation. A proportional dependency was obtained between the energy ratio and a non-dimensional time and this relationship is not dependent on the flow regime; stable displacement or capillary fingering. Experimental results show that for different PTL samples (from different manufacturers) the proportionality is different. The identification of this proportionality allows a unique characterization of PTLs with respect to water transport. This scaling has relevance in porous media flows ranging far beyond fuel cells. In parallel with the experimental analysis, a two-dimensional numerical model was developed in order to simulate the phenomena observed in the experiments. The stochastic nature of the pore size distribution, the role of the PTL wettability and morphology properties on the water transport were analyzed. The effect of a second porous layer placed between the porous transport layer and the catalyst layer called microporous layer, MPL, was also studied. It was found that the presence of the MPL significantly reduced the water content on the PTL by enhancing fingering formation. Moreover, the presence of small defects (cracks) within the MPL was shown to enhance water management. Finally, a corroboration of the numerical simulation was carried out. A threedimensional version of the network model was developed mimicking the experimental conditions. The morphology and wettability of the PTL are tuned to the experiment data by using the new energy scaling of drainage in porous media. Once the fit between numerical and experimental data is obtained, the computational PTL structure can be used in different types of simulations where the conditions are representative of the fuel cell operating conditions.