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Electrolyte additives are generally used in commercial Li-ion cells to improve capacity retention and calendar life. Although it is apparent that electrolyte additives play an important role, the details of how they work are poorly understood. In order to be able to distinguish the effect of an additive on the positive or negative electrodes, an experimental method has been developed based on electrochemical impedance spectroscopy of symmetric cells constructed from electrodes of disassembled full cells similar to the method described by previous workers. This technique proved to be useful and showed that the effects of additives on both electrodes depend strongly on their concentration. It also showed that in some cases, when two additives are introduced in the same cell, both additives contribute to the formation of the surface layer of both electrodes. In other cases, each additive controls the formation of the surface layer of only one electrode.

Biomaterials have been used for more than a century in the human body to improve body functions and replace damaged tissues. Currently approved and commonly used metallic biomaterials such as, stainless steel, titanium, cobalt chromium and other alloys have been found to have adverse effects leading in some cases, to mechanical failure and rejection of the implant. The physical or chemical nature of the degradation products of some implants initiates an adverse foreign body reaction in the tissue. Some metallic implants remain as permanent fixtures, whereas others such as plates, screws and pins used to secure serious fractures are removed by a second surgical procedure after the tissue has healed sufficiently. However, repeat surgical procedures increase the cost of health care and the possibility of patient morbidity. This study focuses on the development of magnesium based biodegradable alloys/metal matrix composites (MMCs) for orthopedic and cardiovascular applications. The Mg alloys/MMCs possessed good mechanical properties and biocompatible properties. Nine different compositions of Mg alloys/MMCs were manufactured and surface treated. Their degradation behavior, ion leaching, wettability, morphology, cytotoxicity and mechanical properties were determined. Alloying with Zn, Ca, HA and Gd and surface treatment resulted in improved mechanical properties, corrosion resistance, reduced cytotoxicity, lower pH and hydrogen evolution. Anodization resulted in the formation of a distinct oxide layer (thickness 5-10 μm) as compared with that produced on mechanically polished samples (~20-50 nm) under ambient conditions. It is envisaged that the findings of this research will introduce a new class of Mg based biodegradable alloys/MMCs and the emergence of innovative cardiovascular and orthopedic implant devices.

Per-Fluoro-Sulphonic-Acid (PFSA) ionomers have been singled out as the preferable ionomers for making the Polymer Electrolyte Membrane Fuel Cells (PEMFC) membranes owing to their extensive intrinsic chemical stability and super sulfonic acid strength which is core to the PEMFC proton conductivity. This thesis presents a deeper analysis into these PFSA ionomer membrane electrode assemblies (MEA), presenting an electrochemical-analytical comparative analysis of the two basic types, which are the Long-Side-Chain (LSC) Nafion® and the ShortSide-Chain (SSC) Aquivion® ionomer MEA with emphasis on performance and durability which are currently not well understood. In particular, electrochemical circuit models and semiempirical models were employed to enable distinguishable comparative analysis. Also, in this thesis, we present a further probe into the effect of ionomer ink making processes, critically investigating the effect of the High Share Dispersion (HSD) process on both the Nafion® and Aquivion® ionomer membrane electrode assembly (MEA). The findings in this research provides a valuable insight into the performance and durability of PFSA ionomer membrane under various application criteria. The effect of operating parameters and accelerated stress testing (AST) on the PFSA ionomers was determined using electrochemical impedance spectroscopy (EIS) and electronic circuit model (ECM) analysis. The result of this study, shows that the ionomer ink making process for Nafion® and Aquivion® MEAs are not transferrable. Analysis of the PEMFC performance upon application of the high shear dispersion (HSD) process showed that Nafion® MEA had a 10.47% increase in voltage while the Aquivion® MEA had a 2.53% decrease in voltage at current density of 1.14A/cm2 . Also, upon accelerated stress testing, the Nafion® showed a 10.49% increase in its voltage while the Aquivion® on the other hand had a 7.16% decrease in voltage at 0.66A/cm2 . Thus indicating the HSD process enhances the performance of the Nafion® MEA and inhibits the performance of the Aquivion® MEA.

Biosensors monitor physiological activities for diagnosis and treatment of disease. Molecularly imprinted polymers (MIPs) are a viable synthetic approach for molecular recognition in biosensing. For biosensing purposes, the most important properties in MIP optimization are sensitivity and selectivity towards a desired analyte. This study aims to optimize MIP sensitivity and selectivity by varying the amount and type of cross-linker used in the synthesis of cortisol and melatonin. The four cross-linkers tested were trimethylpropane trimethacrylate (TRIM), ethyleneglycodimethacrylate (EGDMA), divinylbenzene (DVB), and pentaerythritol triacrylate (PETRA). Based on literature, the following ratios were used for the template molecule to functional monomer to cross-linker in MIP synthesis: for EGDMA cross-linked polymers, 1:6:30; for TRIM and PETRA cross-linked polymers, 1:8:8, 1:6:3, and 1:8:35; for DVB cross-linked polymers, 1:6:30, 1:4:16, and 4:1:60. The polymers were ground and washed, then suspended in a polyvinyl matrix which was spin-coated onto an organic electrochemical transducer (OECT). The device performance was evaluated using electrochemical impedance spectroscopy. For each device, the impedance was measured in electrolyte solutions containing target molecules in concentrations ranging from 1 pM to 100 uM. The impedance was plotted against the analyte concentration to give the sensing slope, which is a measurement for the binding affinity of the polymer. For a device to be considered sensitive, its sensing slope should be greater than its non-imprinted counterpart by a factor above the error margin (+/- 1.79). Of the devices tested, CM1835T (highly cross-linked with TRIM) showed sensitivity towards cortisol, but lacks selectivity towards cortisol over its structural analog, estradiol. Of the melatonin selective polymers, MM163T (low cross-linking with TRIM), MM1630D, and MM4160D (both highly cross-linked with DVB) all showed promising results in sensitivity to melatonin. Overall, the results indicate that high degrees of cross-linking in MIPs improve sensitivity for large, rigid, non-aromatic molecules such as cortisol; however there is no correlation between selectivity and the degree of cross-linking. Meanwhile, divinylbenzene as a cross-linker improves sensitivity and selectivity towards aromatic analytes such as melatonin and estradiol. This study could be improved upon by further characterization of imprinted and non-imprinted polymers, investigation of molecular dynamics, and optimization of devices.

The interconversion of α- and β-Ni(OH)₂ was studied using cyclic voltammetry and dynamic electrochemical impedance (dEIS). Holding experiments were done at 0.5 V, 0.6 V, 0.8 V and 1.0 V while subsequent cathodic holds were applied in selected experiments at -0.1, -0.2, -0.25 V. The number of thickness of Ni(OH)₂ formed increased with increasing anodic potential. After α-Ni(OH)₂ was formed (< 0.5 V), it was easily reduced by sweeping down to -0.15 V. However, sweeping further (> 0.5 V) resulted in its "irreversible" conversion to β-Ni(OH)₂. Since β-Ni(OH)₂ was not reduced by sweeping to -0.15 V, the current, capacitance and the conductance at the α-Ni(OH)₂ peak (at 0.2 V) decreased as a result. However, β-Ni(OH)₂ was shown to be reducible during potential holds at -0.2 V or lower. In contrast, holding at -0.1 V only resulted in partial reduction. Eventually, a link was established between the reduction of β-Ni(OH)₂ and hydrogen evolution. The relatively slow reduction of the β-Ni(OH)₂ to metallic nickel appears to inhibit the capacitance increase at -0.15 V which occurs when the potential is kept under 0.5 V. The retention of a low capacitance while β-Ni(OH)₂ persists suggests a blocking mechanism. A concerted adsorption-desorption step which generates adsorbed hydrogen prior to hydrogen evolution was proposed. An exponential increase in current and capacitance occurred during the potential hold at -0.2 V. The capacitance increase suggests a reversal of the blocking (low capacitance at -0.15 V) caused by the persistence of β-Ni(OH)₂. Additionally, the exponential current decay during the hold at -0.2 V was significantly slower than the conversion of α- to β-Ni(OH)₂ at 0.8 V. This further demonstrates the possibility of a slow step involving surface blocking during the reduction of β-Ni(OH)₂. These observations provide new information on the mechanism and kinetics of the interconversion of α-Ni(OH)₂ into β-Ni(OH)₂ and the interaction of the latter in the hydrogen evolution reaction. / Graduate

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No description available.

State-of-Health (SoH), a specified measure of stability, is a critical parameter for determining the safe operating area of a battery cell and battery packs to avoid abuse and prevent failure and accidents. A series of experiments were performed to evaluate the performance of a 4P1S battery array using electrochemical impedance spectroscopy to identify key frequencies that may describe battery state of health at any state of charge. Using a large sample number of cells, the state of health frequency, fSoH, for these LiFePO4 26650 cells is found to be 158 Hz. Four experiments were performed to evaluate the lifetime in different configurations: single-cell at 1C (2.6A), single-cell at 10C (26A), four cells in parallel at 10C (ideal match), and four cells in parallel (manufacturer match). The lifetime for each experiment set degraded substantially, with the final parallel series reaching end of life at 400 cycles, a 75.32% reduction in life compared to operating solo. Analysis of the fSoH data for these cells revealed a change in imaginary impedance at the critical frequency that corresponded to changes in the capacity and current data, supporting the development of a single-frequency diagnostic tool. An electrochemical model of the battery was generated, and it indicated the anode material was aging faster than the SEI layer, the opposite of normal cell degradation. A post-mortem analysis of cells from three configurations (baseline, single-cell, and parallel-cell) supported the modeling, as physical damage to the copper current collector in the anode was visible in the parallel-connected cell. / Ph. D. / Lithium-ion batteries are used in a large number of applications, from cellular phones to laptops and electric vehicles. In low power devices, such as a laptop, these batteries can be relatively stable if the associated circuitry is designed properly. However, as the amount of power required from the battery increases, the possibility of an internal battery fault will also increase. The ability to determine the stability of the battery for military applications such as laser weapon systems, electromagnetic railguns or commercial systems such as electric vehicles or industrial-scale micro-grids becomes critical to prevent catastrophic events such as fires. Additionally, the ability to determine the battery State-of-Health (SoH), a specified measure of stability, will enable advance warning of a failing battery to optimize the logistics chain in an operational system. A battery marked as “bad” can be scheduled for replacement before a failure actually occurs. This dissertation has designed a series of experiments that establishes the technology to detect these internals faults, and applies them to a scaled battery system that represents a much larger system. When batteries are placed in parallel and discharged at very high currents, typical of the military applications, the lifetime for the cells was reduced by 75% when compared to batteries discharged under the same conditions by themselves. A post-mortem analysis of cells from three different conditions (uncycled, single-cell, parallel-cell) reveals physical damage to the internal electrodes that indicates a high level of internal destruction occurs at high currents when in parallel arrays.

Yes / Electrochemical impedance spectroscopy (EIS) is a technique used to evaluate the electrochemical behavior of metallic materials in different environments. In this study, a mathematical model has been developed to analyse the relationship between solution resistance and concentration conductive-corrosion products (Fe2O3) of metallic corroded materials. This model has been designed as a part of an experimental series to use EIS as a tool for mapping the spatial distribution of corrosion by-product from bridge, in order to evaluate the impact of conductive-corrosion on the properties of the solution. The influence of Fe2O3 on the solution resistance at varying concentrations, has been modelled. Repetitive electrochemical tests were conducted to investigate the relationship between the impedance and concentration in three different concentrations of corrosion by-product. Nyquist and Bode's graphs have been used to quantitatively analyse the EIS data. The implementation of the proposed mathematical model can quantify the solution resistace based on the mass of presented particles, and provide significant efficiency and methodological advancement over EIS technique. The experimental outcomes show a clear link between solution resistance and iron oxide concentration within the solution which is consistent with the model's finding.