The present thesis work is dedicated to the implementation of novel electrochemical methods for the assay of drug compounds such as paracetamol and ascorbic acid and biologically relevant biothiols such as cysteine and glutathione. Particular attention has been paid to the development and application of amperometric detectors allowing for a readily surface renewing and for highly selective and sensitive assays.<p>Coupling of a screen printed electrochemical detector with a monolithic chromatographic column was performed for high-throughput analysis along with selectivity, sensitivity and good precision. The modification of a glassy carbon electrode with a perm-selective membrane was investigated in order to provide an electrochemical sensor for on-site analysis. Acetaminophen was investigated as a model drug compound because of its extensive use in drug “pain killer” medication.<p>Along with the aims of this thesis, a silver polycrystalline electrode was investigated as a sensitive and class selective electrode for the assay of small thiol-based molecules. The silver electrode was implemented for the first time as an amperometric detector coupled to liquid chromatography for the assay of thiols. Application to the study of thiol species present in white wines was realized in order to illustrate the potential of the silver working electrode as amperometric detector. / Doctorat en Sciences biomédicales et pharmaceutiques / info:eu-repo/semantics/nonPublished

Объектом исследования являются электроды на основе нанотубулярного диоксида титана, модифицированные различными способами (термическая обработка, создание композитов с углеродными нанотрубками и частицами металлического никеля). Синтезированные образцы исследовались методом растровой электронной микроскопии и различными электрохимическими методами анализа (гальваностатический заряд-разряд, циклическая вольтамперометрия, импедансная спектроскопия). В результате исследования получены электроды: 1) Т/TiO2-НТ; 2) УНТ/TiO2-НТ; 3) Ni/TiO2-НТ представляющие собой: 1) массивы TiO2-НТ толщиной 3,5 мкм, с внутренним диаметром 70-80 нм и толщиной стенок 30-40 нм; 2) массивы TiO2-НТ с углеродными нанотрубками диаметром 10-30 нм и длиной от десятков нм до десятков мкм на поверхности оксидного слоя; 3) массивы TiO2-НТ, декорированные сферическими наночастицами Ni диаметром 70-100 нм с образованием локальных конгломератов частиц до 500 нм. Результаты работы позволили получить информацию об электрохимических характеристиках синтезированных электродов и преимуществах модификации структур TiO2-НТ для использования их в качестве электродов ионистров. / The object of this research is electrodes based on nanotubular titanium dioxide, modified by various methods (thermal treatment, synthesis of composites with carbon nanotubes and metallic nickel particles). The synthesized samples were investigated by scanning electron microscopy and various electrochemical analysis methods (galvanostatic charge-discharge, cyclic voltammetry, impedance spectroscopy). As a result of the study, were obtained: 1) T/TiO2-NT; 2) CNT/TiO2-NT; 3) Ni/TiO2-NT electrodes, which are: 1) arrays of TiO2-NT 3.5 μm thick, with an inner diameter of 70-80 nm and wall thickness 30-40 nm; 2) arrays of TiO2-NT with carbon nanotubes with a diameter of 10-30 nm and a length from tens of nm to tens of microns on the surface of the oxide layer; 3) arrays of TiO2-NT, decorated with spherical Ni nanoparticles with a diameter of 70-100 nm with the formation of local conglomerates of particles up to 500 nm. The results of the work made it possible to obtain information on the electrochemical characteristics of the synthesized electrodes and the advantages of modifying the TiO2-NT structures to use them as supercapacitor electrodes.

The research discussed is divided into two parts. The first part discusses the background work involved in preparation of the Li-ion cell testing stage. This includes the preparation of anodes using the doctor blade and a calendar mill, electrolyte preparation, test cell assembly, the Li-ion test cell design, and experiments performed to troubleshoot the cell. The second part deals with the cell testing experiments. Li-ion batteries are amongst the most promising rechargeable battery technology because of their high capacity and low weight. Current research aims at improving the anode quality to increase the capacity. The experiments discussed evaluate the traditional anode materials like SFG44 graphite and conducting grade graphite against the novel ones– and tin oxide (SnO2) based and carbon encapsulated tin based anodes. The solid electrolyte interphase formed on each anode was analyzed to understand the initial capacity fade leading to conditioning of the cell thus stabilizing its performance.

Li-ion thin film battery technology has attracted much attention in recent years due to its highest need in portable electronic devices. Development of new materials for lithium ion battery (LIB) is very crucial for enhancement of the performance. LIB can supply higher energy density because Lithium is the most electropositive (-3.04V vs. standard hydrogen electrode) and lightest metal (M=6.94 g/mole). LIBs show many advantages over other kind of batteries such as, high energy density, high power density, long cycle life, no memory effect etc. The major work presented in this thesis is on the development of nanostructured materials for anode of Li-ion battery. It involves the synthesis and analysis of grapheme nanosheet (GNS) and its performance as anode material in Li ion battery. We studied the synthesis of GNS over different substrates and performed the anode studies. The morphology of GNS has great impact on Li storage capacity. Tin and Tin oxide nanostructures have been embedded in the GNS matrix and their electrochemical performance has been studied. Chapter 1 gives the brief introduction about the Li ion batteries (LIBs), working and background. Also the relative advantages and characterization of different electrode materials used in LIBs are discussed. Chapter 2 discusses various experimental techniques that are used to synthesize the electrode materials and characterize them. Chapter3 presents the detailed synthesis of graphene nanosheet (GNS) through electron cyclotron resonance (ECR) microwave plasma enhanced chemical vapor deposition (ECR PECVD) method. Various substrates such as metallic (copper, Ni and Pt coated copper) and insulating (Si, amorphous SiC and Quartz) were used for deposition of GNS. Morphology, structure and chemical bonding were analyzed using SEM, TEM, Raman, XRD and XPS techniques. GNS is a unique allotrope of carbon, which forms highly porous and vertically aligned graphene sheets, which consist of many layers of graphene. The morphology of GNS varies with substrate. Chapter 4 deals with the electrochemical studies of GNS films. The anode studies of GNS over various substrates for Li thin film batteries provides better discharge capacity. Conventional Li-ion batteries that rely on a graphite anode have a limitation in the capacity (372 mAh/g). We could show that the morphology of GNS has great effect in the electrochemical performance and exceeds the capacity limitation of graphite. Among the electrodes PtGNS shown as high discharge capacity of ~730 mAh/g compare to CuGNS (590 mAh/g) and NiGNS (508 mAh/g) for the first cycle at a current density of 23 µA/cm2. Electrochemical impedance spectroscopy provides the various cell parameters of the electrodes. Chapter 5 gives the anodic studies of Tin (Sn) nanoparticles decorated over GNS matrix. Sn nanoparticles of 20 to 100nm in size uniformly distributed over the GNS matrix provides a discharge capacity of ~1500 mAh/g mAh/g for as deposited and ~950 mAh/g for annealed Sn@GNS composites, respectively. The cyclic voltammogram (CV) also shows the lithiation and delithiation process on GNS and Sn particles. Chapter 6 discusses the synthesis of Tinoxide@GNS composite and the details of characterization of the electrode. SnO and SnO2 phases of Tin oxide nanostructures differing in morphologies were embedded in the GNS matrix. The anode studies of the electrode shows a discharge capacity of ~1400 mAh/g for SnO phase (platelet morphology) and ~950 mAh/g for SnO2 phase (nanoparticle morphology). The SnO phase also exhibits a good coulumbic efficiency of ~95%. Chapter 7 describes the use of SnO2 nanowire attached to the side walls of the GNS matrix. A discharge capacity of ~1340 mAh/g was obtained. The one dimensional wire attached to the side walls of GNS film and increases the surface area of active material for Li diffusion. Discharge capacity obtained was about 1335 mAhg-1 and the columbic efficiency of ~86% after the 50th cycle. The research work carried out as part of this thesis, and the results have summarized in chapter 8.

Indiana University-Purdue University Indianapolis (IUPUI) / Since 1990s, rechargeable Li-ion batteries have been widely used in consumer electronics such as cell phones, global positioning systems (GPS), personnel digital assistants (PDA), digital cameras, and laptop computers. Recently Li-ion batteries received considerable attention as a major power source for electric vehicles. However, significant technical challenges still exist for widely deploying Li-ion batteries in electric vehicles. For instance, the energy density of Li-ion batteries is not high enough to support a long-distance commute. The Li-ion batteries used for the Nissan Leaf and Chevy Volt only can support 50 – 100 miles per charge. The cost of Li-ion battery packs in electric vehicles is still high. The battery pack for the Chevy Volt costs about $8,000, and the larger one in the Nissan Leaf costs about $12,000. To address these problems, new Li-ion battery electrode materials with high energy density and low cost should be developed. Among Li-ion battery cathode materials, vanadium pentoxide, V2O5, is one of the earliest oxides studied as a cathode for Li-ion batteries because of its low cost, abundance, easy synthesis, and high energy density. However, its practical reversible capacity has been limited due to its irreversible structural change when Li insertion is more than x = 1. Tremendous efforts have been made over the last twenty years to improve the phase reversibility of LixV2O5 (e.g., 0 ≤ x ≤ 2) because of vanadium pentoxides’ potential use as high capacity cathodes in Li-ion batteries. In this thesis, a new strategy was studied to develop vanadium pentoxide cathode materials with improved phase reversibility. The first study is to synthesize vanadium oxide cathodes via a new chemical route – creating a phase transformation from the vanadium sulfide to oxide. The β-Na0.33V2O5 was prepared via a new method of chemical synthesis, involving the chemical transformation of NaVS2 via heat-treatment at 600 °C in atmospheric air. The β-Na0.33V2O5 particles were well crystalized and rod-shaped, measuring 7–15 μm long and 1–3 μm wide with the formation of the crystal defects on the surface of the particles. In contrast to previous reports contained in the literature, Na ions were extracted, without any structural collapse, from the β -Na0.33V2O5 structure and replaced with Li ions during cycling of the cell in the voltage range, 1.5 V to 4.5 V. This eventually resulted in a fully reversible Li intercalation into the LixV2O5 structure when 0.0 ≤ x ≤ 2.0. The second study is to apply the synthesis method to LiVS2 for the synthesis of β׳-LixV2O5 for use as a high performance cathode. The synthesis method is based on the heat treatment of the pure LiVS2 in atmospheric air. By employing this method of synthesis, well-crystalized, rod-shaped β׳-LixV2O5 particles 20 – 30 μm in length and 3 – 6 μm in width were obtained. Moreover, the surface of β׳-LixV2O5 particles was found to be coated by an amorphous vanadium oxysulfide film (~20 nm in thickness). In contrast to a low temperature vanadium pentoxide phase (LixV2O5), the electrochemical intercalation of lithium into the β׳-LixV2O5 was fully reversible where 0.0 < x < 2.0, and it delivered a capacity of 310 mAh/g at a current rate of 0.07 C between 1.5 V and 4 V. Good capacity retention of more than 88% was also observed after 50 cycles even at a higher current rate of 2 C. The third study is the investigation of NaVS2 as a cathode intercalation material for sodium ion batteries. We have shown that reversible electrochemical deintercalation of x ~ 1.0 Na per formula unit of NaxVS2, corresponding to a capacity of ~200 mAh/g, is possible. And a stable capacity of ~120 mAh/g after 30 cycles was observed. These studies show that the new chemical synthesis route for creating a phase transformation from the vanadium sulfide to oxide by heat treatment in air is a promising method for preparing vanadium oxide cathode material with high reversibility. Although this sample shows a relatively low voltage range compared with other cathodes such as LiCoO2 (3.8 V) and LiFePO4 (3.4 V), the large capacity of this sample is quite attractive in terms of increasing energy density in Li-ion batteries. Also, NaVS2 could be a promising cathode material for sodium ion batteries.

Indiana University-Purdue University Indianapolis (IUPUI) / In recent years, magnesium alloys, due to their high strength and biocompatibility, have attracted significant interest in medical applications, such as cardiovascular stents, orthopedic implants, and devices. To overcome the high corrosion rate of magnesium alloys, coatings have been developed on the alloy surface. Most coating methods, such as anodic oxidation, polymer coating and chemical conversion coating, cannot produce satisfactory coating to be used in human body environment. Recent studies demonstrate that micro-arc oxidation (MAO) technique can produce hard, dense, wear-resistant and well-adherent oxide coatings for light metals such as aluminum, magnesium, and titanium. Though there are many previous studies, the understanding of processing conditions on coating performance remains elusive. Moreover, previous tests were done in simulated body fluid. No test has been done in a cell culture medium, which is much closer to human body environment than simulated body fluid. In this study, the effect of MAO processing time (1 minute, 5 minutes, 15 minutes, and 20 minutes) on the electrochemical behaviors of the coating in both conventional simulated body fluid and a cell culture medium has been investigated. Additionally a new electrolyte (12 g/L Na2SiO3, 4 g/L NaF and 4 ml/L C3H8O3) has been used in the MAO coating process. Electrochemical behaviors were measured by performing potentiodynamic polarization and electrochemical impedance spectroscopy tests. In addition to the tests in simulated body fluid, the MAO-coated and uncoated samples were immersed in a cell culture medium to investigate the corrosion behaviors and compare the difference in these two kinds of media. The results show that in the immersion tests in conventional simulated body fluid, the 20-minute MAO coated sample has the best resistance to corrosion due to the largest coating thickness. In contrast, in the cell culture medium, all MAO coated samples demonstrate a similar high corrosion resistance behavior, independent of MAO processing time. This is probably due to the organic passive layers formed on the coating surfaces. Additionally, a preliminary finite element model has been developed to simulate the immersion test of magnesium alloy in simulated body fluid. Comparison between the predicted corrosion current density and experimental data is discussed.

Indiana University-Purdue University Indianapolis (IUPUI) / Lithium ion (Li-ion) batteries have become integral parts of our lives; they are widely used in applications like handheld consumer products, automotive systems, and power tools among others. To extract maximum output from a Li-ion battery under optimal conditions it is imperative to have access to the state of the battery under every operating condition. Faults occurring in the battery when left unchecked can lead to irreversible, and under extreme conditions, catastrophic damage. In this thesis, an adaptive fault diagnosis technique is developed for Li-ion batteries. For the purpose of fault diagnosis the battery is modeled by using lumped electrical elements under the equivalent circuit paradigm. The model takes into account much of the electro-chemical phenomenon while keeping the computational effort at the minimum. The diagnosis process consists of multiple models representing the various conditions of the battery. A bank of observers is used to estimate the output of each model; the estimated output is compared with the measurement for generating residual signals. These residuals are then used in the multiple model adaptive estimation (MMAE) technique for generating probabilities and for detecting the signature faults. The effectiveness of the fault detection and identification process is also dependent on the model uncertainties caused by the battery modeling process. The diagnosis performance is compared for both the linear and nonlinear battery models. The non-linear battery model better captures the actual system dynamics and results in considerable improvement and hence robust battery fault diagnosis in real time. Furthermore, it is shown that the non-linear battery model enables precise battery condition monitoring in different degrees of over-discharge.

Indiana University-Purdue University Indianapolis (IUPUI) / There is a strong urge for advanced diagnosis method, especially in high power battery packs and high energy density cell design applications, such as electric vehicle (EV) and hybrid electric vehicle segment, due to safety concerns. Accurate and robust diagnosis methods are required in order to optimize battery charge utilization and improve EV range. Battery faults cause significant model parameter variation affecting battery internal states and output. This work is focused on developing diagnosis method to reliably detect various faults inside lithium-ion cell using electrochemical model based observer and fuzzy logic algorithm, which is implementable in real-time. The internal states and outputs from battery plant model were compared against those from the electrochemical model based observer to generate the residuals. These residuals and states were further used in a fuzzy logic based residual evaluation algorithm in order to detect the battery faults. Simulation results show that the proposed methodology is able to detect various fault types including overcharge, over-discharge and aged battery quickly and reliably, thus providing an effective and accurate way of diagnosing li-ion battery faults.