SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

EXPERIMENTAL INVESTIGATION INTO PARTICULATE MATTER DISTRIBUTION IN CATALYZED PARTICULATE FILTERS USING A 3D TERAHERTZ WAVE SCANNER

The particulate matter distribution (PM) trends that exist in catalyzed particulate filters (CPFs) after loading, passive oxidation, active regeneration, and post loading conditions are not clearly understood. These data are required to optimize the operation of CPFs, prevent damage to the CPFs caused by non-uniform distributions, and develop accurate CPF models. To develop an understanding of PM distribution trends, multiple tests were conducted and the PM distribution was measured in three dimensions using a terahertz wave scanner. The results of this work indicate that loading, passive oxidation, active regeneration, and post loading can all cause non-uniform PM distributions. The density of the PM in the substrate after loading and the amount of PM that is oxidized during passive oxidations and active regenerations affect the uniformity of the distribution. Post loading that occurs after active regenerations result in distributions that are less uniform than post loading that occurs after passive oxidations.

Assessing the contribution of microgrids to the reliability of distribution networks

The emergence of microgeneration has recently lead to the concept of microgrid, a network of LV consumers and producers able to export electric energy in some circumstances and also to work in an isolated way in emergency situations. Research on the organization of microgrids, control devices, functionalities and other technical aspects is presently being carried out, in order to establish a consistent technical framework to support the concept. The successful development of the microgrid concept implies the definition of a suitable regulation for its integration on distribution systems. In order to define such a regulation, the identification of costs and benefits that microgrids may bring is a crucial task. Actually, this is the basis for a discussion about the way global costs could be divided among the different agents that benefit from the development of microgrids. Among other aspects, the effect of microgrids on the reliability of the distribution network has been pointed out as an important advantage, due to the ability of isolated operation in emergency situations. This paper identifies the situations where the existence of a microgrid may reduce the interruption rate and duration and thus improve the reliability indices of the distribution network. The relevant expressions necessary to quantify the reliability are presented. An illustrative example is included, where the global influence of the microgrid in the reliability is commented.

Frequency adjustable MEMS vibration energy harvester

Ambient mechanical vibrations offer an attractive solution for powering the wireless sensor nodes of the emerging "Internet-of-Things". However, the wide-ranging variability of the ambient vibration frequencies pose a significant challenge to the efficient transduction of vibration into usable electrical energy. This work reports the development of a MEMS electromagnetic vibration energy harvester where the resonance frequency of the oscillator can be adjusted or tuned to adapt to the ambient vibrational frequency. Micro-fabricated silicon spring and double layer planar micro-coils along with sintered NdFeB micro-magnets are used to construct the electromagnetic transduction mechanism. Furthermore, another NdFeB magnet is adjustably assembled to induce variable magnetic interaction with the transducing magnet, leading to significant change in the spring stiffness and resonance frequency. Finite element analysis and numerical simulations exhibit substantial frequency tuning range (25% of natural resonance frequency) by appropriate adjustment of the repulsive magnetic interaction between the tuning and transducing magnet pair. This demonstrated method of frequency adjustment or tuning have potential applications in other MEMS vibration energy harvesters and micromechanical oscillators.

Integrated CoPtP permanent magnets for MEMS electromagnetic energy harvesting applications

This work reports the development of integrated Co rich CoPtP hard magnetic material for MEMS applications such as Electromagnetic Vibration Energy Harvesting. We report a new method of electrodeposition compared to the conventional DC plating, involving a combination of forward and reverse pulses for optimized deposition of Co rich CoPtP hard magnetic material. This results in significant improvements in the microstructure of the developed films as the pulse reverse plated films are smooth, stress free and uniform. Such improvements in the structural properties are reflected in the hard magnetic properties of the material as well. The intrinsic coercivities of the pulse reverse deposited film are more than 6 times higher for both in-plane and out-of-plane measurement directions and the squareness of the hysteresis loops also improve due to the similar reasons.

A low frequency MEMS energy harvester scavenging energy from magnetic field surrounding an AC current-carrying wire

This paper reports on a low frequency piezoelectric energy harvester that scavenges energy from a wire carrying an AC current. The harvester is described, fabricated and characterized. The device consists of a silicon cantilever with integrated piezoelectric capacitor and proof-mass that incorporates a permanent magnet. When brought close to an AC current carrying wire, the magnet couples to the AC magnetic field from a wire, causing the cantilever to vibrate and generate power. The measured average power dissipated across an optimal resistive load was 1.5 μW. This was obtained by exciting the device into mechanical resonance using the electro-magnetic field from the 2 A source current. The measurements also reveal that the device has a nonlinear response that is due to a spring hardening mechanism.

Otter (Lutra lutra) distribution modeling at two resolution scales suited to conservation planning in the Iberian Peninsula

We used the results of the Spanish Otter Survey of 1994–1996, a Geographic Information System and stepwise multiple logistic regression to model otter presence/absence data in the continental Spanish UTM 10 10-km squares. Geographic situation, indicators of human activity such as highways and major urban centers, and environmental variables related with productivity, water availability, altitude, and environmental energy were included in a logistic model that correctly classified about 73% of otter presences and absences. We extrapolated the model to the adjacent territory of Portugal, and increased the model’s spatial resolution by extrapolating it to 1 1-km squares in the whole Iberian Peninsula. The model turned out to be rather flexible, predicting, for instance, the species to be very restricted to the courses of rivers in some areas, and more widespread in others. This allowed us to determine areas where otter populations may be more vulnerable to habitat changes or harmful human interventions. # 2003 Elsevier Ltd. All rights reserved.

Revisiting compressed air energy storage.

The use of renewable energies as a response to the EU targets defined for 2030 Climate Change and Energy has been increasing. Also non-dispatchable and intermittent renewable energies like wind and solar cannot generally match supply and demand, which can also cause some problems in the grid. So, the increased interest in energy storage has evolved and there is nowadays an urgent need for larger energy storage capacity. Compressed Air Energy Storage (CAES) is a proven technology for storing large quantities of electrical energy in the form of high-pressure air for later use when electricity is needed. It exists since the 1970’s and is one of the few energy storage technologies suitable for long duration (tens of hours) and utility scale (hundreds to thousands of MW) applications. It is also one of the most cost-effective solutions for large to small scale storage applications. Compressed Air Energy Storage can be integrated and bring advantages to different levels of the electric system, from the Generation level, to the Transmission and Distribution levels, so in this paper a revisit of CAES is done in order to better understand what and how it can be used for our modern needs of energy storage.

Clinical Accuracy of the MedGem Indirect Calorimeter for Measuring Resting Energy Expenditure in Cancer Patients

OBJECTIVE: To compare, in patients with cancer and in healthy subjects, measured resting energy expenditure (REE) from traditional indirect calorimetry to a new portable device (MedGem) and predicted REE. DESIGN: Cross-sectional clinical validation study. SETTING: Private radiation oncology centre, Brisbane, Australia. SUBJECTS: Cancer patients (n = 18) and healthy subjects (n = 17) aged 37-86 y, with body mass indices ranging from 18 to 42 kg/m(2). INTERVENTIONS: Oxygen consumption (VO(2)) and REE were measured by VMax229 (VM) and MedGem (MG) indirect calorimeters in random order after a 12-h fast and 30-min rest. REE was also calculated from the MG without adjustment for nitrogen excretion (MGN) and estimated from Harris-Benedict prediction equations. Data were analysed using the Bland and Altman approach, based on a clinically acceptable difference between methods of 5%. RESULTS: The mean bias (MGN-VM) was 10% and limits of agreement were -42 to 21% for cancer patients; mean bias -5% with limits of -45 to 35% for healthy subjects. Less than half of the cancer patients (n = 7, 46.7%) and only a third (n = 5, 33.3%) of healthy subjects had measured REE by MGN within clinically acceptable limits of VM. Predicted REE showed a mean bias (HB-VM) of -5% for cancer patients and 4% for healthy subjects, with limits of agreement of -30 to 20% and -27 to 34%, respectively. CONCLUSIONS: Limits of agreement for the MG and Harris Benedict equations compared to traditional indirect calorimetry were similar but wide, indicating poor clinical accuracy for determining the REE of individual cancer patients and healthy subjects.