Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.

CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Multilevel converters in renewable energy systems

In photovoltaic, fuel cells and storage batteries, the low output DC voltage should be boosted. Therefore, a step-up converter is necessary to boost the low DC voltage for the DC link voltage of the inverter. The main contribution of this chapter is to electrical energy conversion in renewable energy systems based on multilevel inverters. Different configuration of renewable energy systems based on power converters will be discussed in detail. Finally, a new single inductor Multi-Output Boost (MOB) converter is proposed, which is compatible with the diode-clamped configuration. Steady state and dynamic analyses have been carried out in order to show the validity of the proposed topology. Then the joint circuit of the proposed DC-DC converter with a three-level diode-clamped converter is presented in order to have a series regulated voltage at the DC link voltage of the diode-clamped inverter. MOB converter can boost the low input DC voltage of the renewable energy sources and at the same time adjust the voltage across each capacitor to the desired voltage levels, thereby solving the main problem associated with capacitor voltage imbalance in this type of multilevel converter.

Characteristics of sustainable entrepreneurship : some early explorations from the CAUSEE study

Principal Topic: For forward thinking companies, the environment may represent the ''biggest opportunity for enterprise and invention the industrial world has ever seen'' (Cairncross 1990). Increasing awareness of environmental and sustainability issues through media including the promotion of Al Gore's ''An Inconvenient Truth'' has seen increased awareness of environmental and sustainability issues and increased demand for business processes that reduce detrimental environmental impacts of global development (Dean & McMullen 2007). The increased demand for more environmentally sensitive products and services represents an opportunity for the development of ventures that seek to satisfy this demand through entrepreneurial action. As a consequence, increasing recent market developments in renewable energy, carbon emissions, fuel cells, green building, and other sectors suggest an increasing importance of opportunities for environmental entrepreneurship (Dean and McMullen 2007) and increasingly important area of business activity (Schaper 2005). In the last decade in particular, big business has sought to develop a more ''sustainability/ green friendly'' orientation as a response to public pressure and increased government legislation and policy to improve environmental performance (Cohen and Winn 2007). Whilst much of the literature and media is littered with examples of sustainability practices of large firms, nascent and young sustainability firms have only recently begun generating strong research and policy interest (Shepherd, Kuskova and Patzelt 2009): not only for their potential to generate above average financial performance and returns owing to a greater popularity and demand towards sustainability products and services offerings, but also for their intent to lessen environmental impacts, and to provide a more accurate reflection of the ''true cost'' of market offerings taking into account carbon and environmental impacts. More specifically, researchers have suggested that although the previous focus has been on large firms and their impact on the environment, the estimated collective impact of entries and exits of nascent and young firms in development is substantial and could outweigh the combined environmental impact of large companies (Hillary, 2000). Therefore, it may be argued that greater attention should be paid to nascent and young firms and researching sustainability practices, for both their impact in reducing environmental impacts and potential higher financial performance. Whilst acknowledging this research only uses the first wave of a four year longitudinal study of nascent and young firms, it can still begin to provide initial analysis on which to continue further research. The aim of this paper therefore is to provide an overview of the emerging literature in sustainable entrepreneurship and to present some selected preliminary results from the first wave of the data collection, with comparison, where appropriate, of sustainable and firms that do not fulfil this criteria. ''One of the key challenges in evaluating sustainability entrepreneurship is the lack of agreement in how it is defined'' (Schaper, 2005: 10). Some evaluate sustainable entrepreneurs simply as one category of entrepreneurs with little difference between them and traditional entrepreneurs (Dees, 1998). Other research recognises values-based sustainable enterprises requiring a unique perspective (Parrish, 2005). Some see the environmental or sustainable entrepreneurship is a subset of social entrepreneurship (Cohen & Winn, 2007; Dean & McMullen, 2007) whilst others see it as a separate, distinct theory (Archer 2009). Following one of the first definitions of sustainability developed by the Brundtland Commission (1987) we define sustainable entrepreneurship as firms which ''seek to meet the needs and aspirations of the present without compromising the ability to meet those of the future''. ---------- Methodology/Key Propositions: In this exploratory paper we investigate sustainable entrepreneurship using Cohen et al.'s (2008) framework to identify strategies of nascent and young entrepreneurial firms. We use data from The Comprehensive Australian Study of Entrepreneurial Emergence (CAUSEE). This study shares the general empirical approach with PSED studies in the US (Reynolds et al 1994; Reynolds & Curtin 2008). The overall study uses samples of 727 nascent (not yet operational) firms and another 674 young firms, the latter being in an operational stage but less than four years old. To generate the sub sample of sustainability firms, we used content analysis techniques on firm titles, descriptions and product descriptions provided by respondents. Two independent coders used a predefined codebook developed from our review of the sustainability entrepreneurship literature (Cohen et al. 2009) to evaluate the content based on terms such as ''sustainable'' ''eco-friendly'' ''renewable energy'' ''environment'' amongst others. The inter-rater reliability was checked and the Kappa's co-efficient was found to be within the acceptable range (0.746). 85 firms fulfilled the criteria given for inclusion in the sustainability cohort. ---------- Results and Implications: The results for this paper are based on Wave one of the CAUSEE survey which has been completed and the data is available for analysis. It is expected that the findings will assist in beginning to develop an understanding of nascent and young firms that are driven to contribute to a society which is sustainable, not just from an economic perspective (Cohen et al 2008), but from an environmental and social perspective as well. The CAUSEE study provides an opportunity to compare the characteristics of sustainability entrepreneurs with entrepreneurial firms without a stated environmental purpose, which constitutes the majority of the new firms created each year, using a large scale novel longitudinal dataset. The results have implications for Government in the design of better conditions for the creation of new business, firms who assist sustainability in developing better advice programs in line with a better understanding of their needs and requirements, individuals who may be considering becoming entrepreneurs in high potential arenas and existing entrepreneurs make better decisions.

Modeling, stability analysis and control of microgrid

With the increase in the level of global warming, renewable energy based distributed generators (DGs) will increasingly play a dominant role in electricity production. Distributed generation based on solar energy (photovoltaic and solar thermal), wind, biomass, mini-hydro along with use of fuel cells and micro turbines will gain considerable momentum in the near future. A microgrid consists of clusters of load and distributed generators that operate as a single controllable system. The interconnection of the DG to the utility/grid through power electronic converters has raised concern about safe operation and protection of the equipments. Many innovative control techniques have been used for enhancing the stability of microgrid as for proper load sharing. The most common method is the use of droop characteristics for decentralized load sharing. Parallel converters have been controlled to deliver desired real power (and reactive power) to the system. Local signals are used as feedback to control converters, since in a real system, the distance between the converters may make the inter-communication impractical. The real and reactive power sharing can be achieved by controlling two independent quantities, frequency and fundamental voltage magnitude. In this thesis, an angle droop controller is proposed to share power amongst converter interfaced DGs in a microgrid. As the angle of the output voltage can be changed instantaneously in a voltage source converter (VSC), controlling the angle to control the real power is always beneficial for quick attainment of steady state. Thus in converter based DGs, load sharing can be performed by drooping the converter output voltage magnitude and its angle instead of frequency. The angle control results in much lesser frequency variation compared to that with frequency droop. An enhanced frequency droop controller is proposed for better dynamic response and smooth transition between grid connected and islanded modes of operation. A modular controller structure with modified control loop is proposed for better load sharing between the parallel connected converters in a distributed generation system. Moreover, a method for smooth transition between grid connected and islanded modes is proposed. Power quality enhanced operation of a microgrid in presence of unbalanced and non-linear loads is also addressed in which the DGs act as compensators. The compensator can perform load balancing, harmonic compensation and reactive power control while supplying real power to the grid A frequency and voltage isolation technique between microgrid and utility is proposed by using a back-to-back converter. As utility and microgrid are totally isolated, the voltage or frequency fluctuations in the utility side do not affect the microgrid loads and vice versa. Another advantage of this scheme is that a bidirectional regulated power flow can be achieved by the back-to-back converter structure. For accurate load sharing, the droop gains have to be high, which has the potential of making the system unstable. Therefore the choice of droop gains is often a tradeoff between power sharing and stability. To improve this situation, a supplementary droop controller is proposed. A small signal model of the system is developed, based on which the parameters of the supplementary controller are designed. Two methods are proposed for load sharing in an autonomous microgrid in rural network with high R/X ratio lines. The first method proposes power sharing without any communication between the DGs. The feedback quantities and the gain matrixes are transformed with a transformation matrix based on the line R/X ratio. The second method involves minimal communication among the DGs. The converter output voltage angle reference is modified based on the active and reactive power flow in the line connected at point of common coupling (PCC). It is shown that a more economical and proper power sharing solution is possible with the web based communication of the power flow quantities. All the proposed methods are verified through PSCAD simulations. The converters are modeled with IGBT switches and anti parallel diodes with associated snubber circuits. All the rotating machines are modeled in detail including their dynamics.

Is globalisation an enabler of radical innovation in Toyota?

Prior evidence from the fields of innovation management and supplier relations predicts that Japanese firms should be naturally disadvantaged in developing and deploying radical innovations. But this conclusion is inconsistent with recent developments in the automotive industry. This paper presents secondary case study data focusing on fuel cell powered vehicles and hybrid cars to show that Toyota, one of Japan's largest and most influential corporations, is capable of developing radically new technologies, and is in several respects better at this sort of innovation than the rest of the global automotive industry.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Cascaded DC-DC converter connection of photovoltaic modules

New residential scale photovoltaic (PV) arrays are commonly connected to the grid by a single dc-ac inverter connected to a series string of pv panels, or many small dc-ac inverters which connect one or two panels directly to the ac grid. This paper proposes an alternative topology of nonisolated per-panel dc-dc converters connected in series to create a high voltage string connected to a simplified dc-ac inverter. This offers the advantages of a "converter-per-panel" approach without the cost or efficiency penalties of individual dc-ac grid connected inverters. Buck, boost, buck-boost, and Cu´k converters are considered as possible dc-dc converters that can be cascaded. Matlab simulations are used to compare the efficiency of each topology as well as evaluating the benefits of increasing cost and complexity. The buck and then boost converters are shown to be the most efficient topologies for a given cost, with the buck best suited for long strings and the boost for short strings. While flexible in voltage ranges, buck-boost, and Cu´k converters are always at an efficiency or alternatively cost disadvantage.

Galvanic replacement mediated synthesis of hollow Pt nanocatalysts : significance of residual Ag for the H2 evolution reaction

With the increasing popularity of the galvanic replacement approach towards the development of bimetallic nanocatalysts, special emphasis has been focused on minimizing the use of expensive metal (e.g. Pt), in the finally formed nanomaterials (e.g. Ag/Pt system as a possible catalyst for fuel cells). However, the complete removal of the less active sacrificial template is generally not achieved during galvanic replacement, and its residual presence may significantly impact on the electrocatalytic properties of the final material. Here, we investigate the hydrogen evolution reaction (HER) activity of Ag nanocubes replaced with different amounts of Pt, and demonstrate how the bimetallic composition significantly affects the activity of the alloyed nanomaterial.