Thesis advisor: Dunwei Wang / Non-aqueous Li-O2 batteries promise the highest theoretical specific energy among all rechargeable batteries. It is the only candidate that can be comparable with the internal combustion engine in terms of gravimetric energy density. This makes Li-O2 batteries preferable in the application of electric vehicles or drones. However, the materialization of this technology has been hindered by the poor cycling performance. The major reason for the degradation of the battery at the current research stage has been identified as the decomposition of the electrolyte and the cathode. These parasitic reactions will lower the yield of the desired product and induce huge overpotential during the recharge process. By carefully examining the degradation mechanism, we have identified the reactive oxygen species as the culprit that will corrode the cathode and attack the organic solvents. While parallel efforts have been devoted to reduce the reactivity of these species toward electrolyte, the main focus of this thesis is to identify suitable material platforms that can provide optimum performance and stability as cathodes. A bio-inspired wood-derived N-doped carbon is first introduced to demonstrate the benefit of hierarchical pore structures for Li-O2 cathodes. But the instability of the carbon cathode itself limits the lifetime of the battery. To improve the stability of carbon, we further introduce a catalytic active surface coating of FeOx on a three dimensionally ordered mesoporous carbon. The isolation of carbon from the reactive intermediates greatly improves the stability of the cathode. Yet the imperfections of the protection layer on carbon calls for a stable substrate that can replace carbon. TiSi2 is explored as the candidate. With the decoration of Pd catalysts, the Pd/TiSi2 cathode can provide extraordinary stability toward reactive oxygen species. But this composite cathode suffers from the detachment of the Pd catalyst. A Co3O4 surface layer is further introduced to enhance the adhesion of the catalyst, which doubles the lifetime of the cathode. To achieve a fully stable cathode, Ru catalyst with stronger adhesion on TiSi2 directly is explored and identified to be robust in the operating conditions of Li-O2 batteries. The expedition for stable cathodes in Li-O2 batteries is expected to provide a clean material platform. This platform can simplify the study in evaluating the effectiveness of catalysts, the reaction mechanism at the cathode and the stability of the electrolyte. Toward the end of this thesis, an exploration is made to enable rechargeable Mg metal battery with a conversion Br2 cathode. This new system can avoid the dendritic growth of Li metal by the adoption of Mg as the anode and can promise better cathode kinetics by forming a soluble discharge product. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / The performance of advanced energy storage devices is intimately connected to the designs of electrodes. To enable significant developments in this research field, we need detailed information and knowledge about how the functions and performances of the electrodes depend on their chemical compositions, dimensions, morphologies, and surface properties. This thesis presents my successes in synthesizing and characterizing electrode materials for advanced electrochemical energy storage devices, with much attention given to understanding the operation and fading mechanism of battery electrodes, as well as methods to improve their performances and stabilities. This dissertation is presented within the framework of two energy storage technologies: lithium ion batteries and lithium oxygen batteries. The energy density of lithium ion batteries is determined by the density of electrode materials and their lithium storage capabilities. To improve the overall energy densities of lithium ion batteries, silicon has been proposed to replace lithium intercalation compounds in the battery anodes. However, with a ~400% volume expansion upon fully lithiation, silicon-based anodes face serious capacity degradation in battery operation. To overcome this challenge, heteronanostructure-based Si/TiSi2 were designed and synthesized as anode materials for lithium ion batteries with long cycling life. The performance and morphology relationship was also carefully studied through comparing one-dimensional and two-dimensional heteronanostructure-based silicon anodes. Lithium oxygen batteries, on the other hand, are devices based on lithium conversion chemistries and they offer higher energy densities compared to lithium ion batteries. However, existing carbon based electrodes in lithium oxygen batteries only allow for battery operation with limited capacity, poor stability and low round-trip efficiency. The degradation of electrolytes and carbon electrodes have been found to both contribute to the challenges. The understanding of the synergistic effect between electrolyte decomposition and electrode decomposition, nevertheless, is conspicuously lacking. To better understand the reaction chemistries in lithium oxygen batteries, I designed, synthesized, and studied heteronanostructure-based carbon-free inorganic electrodes, as well as carbon electrodes whose surfaces protected by metal oxide thin films. The new types of electrodes prove to be highly effective in minimizing parasitic reactions, reducing operation overpotentials and boosting battery lifetimes. The improved stability and well-defined electrode morphology also enabled detailed studies on the formation and decomposition of Li2O2. To summarize, this dissertation presented the synthesis and characterization of inorganic nanostructured materials for advanced energy storage. On a practical level, the new types of materials allow for the immediate advancement of the energy storage technology. On a fundamental level, it helped to better understand reaction chemistries and fading mechanisms of battery electrodes. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Este trabalho buscou primeiramente caracterizar passivos ambientais em empreendimentos energéticos, em especial nos de armazenamento de energia. Para isto, avaliou-se as atividades potenciais de contaminação em empreendimentos com armazenamento de energia, em qualquer uma de suas formas (energia eletroquímica, elétrica, mecânica, cinética, hidráulica, térmica, química e nuclear). Foi elaborada uma sequência metodológica de levantamento de informações, com posterior associação entre os contaminantes e as atividades fonte de contaminação. Para um dos tipos de fontes de contaminação através de combustíveis, foi realizado um ensaio de bancada com amostras de combustível diluídas em água, para avaliar em laboratório se somente os compostos BTEX e PAH estão presentes, uma vez que são os geralmente analisados em áreas de armazenamento de gasolina e diesel, objetivando mensurar se a análise de somente estes compostos são suficientes para abranger o potencial toxicológico dessa contaminação. Como resultado constatou-se a necessidade de incluir os Trimetilbenzenos nas análises padrão realizadas nas áreas de armazenamento dos combustíveis avaliados. Para os mesmos tipos de contaminantes, os derivados de combustíveis, foram realizadas campanhas de oxidação química (ISCO) num posto de combustíveis desativado através da injeção de oxidante no aquífero freático, buscando a redução das concentrações para a intervenção de obras civis de uma nova ocupação para o imóvel. Os resultados obtidos foram satisfatórios, atendendo os objetivos pré-definidos, demonstrando a eficácia do processo oxidativo para a degradação de derivados de combustíveis utilizando-se o Persulfato de Sódio, ativado tanto por metais complexados (FeEDTA) quanto por aplicação em meio alcalino. / This study sought initially to characterize environmental liabilities in energy enterprises, especially in energy storage ones. Therefore, we evaluated the potential contamination activities within developments with energy storage in any of its forms (electrochemical, electrical, mechanical, kinetic, hydraulic, thermal, chemical and nuclear energy). A survey was elaborated using a methodological sequence to gather information, with subsequent association between the contaminant and the source of contamination activities. For one of the types of sources of contamination by fuel, we performed a bench and lab test using fuel diluted in water samples to evaluate if only the BTEX and HPA compounds, usually analyzed in areas of gasoline and diesel storage, are sufficient to cover the toxicological potential of such contamination. The results suggested the need to include trimethylbenzene in the standard analysis performed in the fuel storage areas evaluated. For the same types of contaminants, derivatives of fuels, chemical oxidation campaigns (ISCO) were carried out using direct push injections at a deactivated gas station, seeking to reduce concentrations for the intervention of civil works for a new occupation of the land. The results were satisfactory and the proposed goals have been achieved demonstrating the effectiveness of the oxidation process for the degradation of derived of fuels by using the Sodium Persulfate, activated by complexed metals (FeEDTA) and also by application in alkaline environment.

Microgrids are local power systems of different sizes located inside the distribution systems. Each microgrid contains a group of interconnected loads and distributed energy resources that acts as a single controllable entity with respect to the grid. Their islanding operation capabilities during emergencies improve the resiliency and reliability of the electric energy supply. Due to its low kinetic energy storage capacity, maintaining microgrid stability is challenging under system contingencies and unpredictable power generation from renewable resources. This dissertation highlights the potential benefits of flexibly utilizing the battery energy storage systems to enhance the stability of microgrids. The main contribution of this research consists in the development of a storage converter controller with an additional stability margin that enables it to improve microgrid frequency and voltage regulation as well as its induction motor post-fault speed recovery. This new autonomous control technique is implemented by adaptively setting the converter controller parameters based on its estimated phase-locked loop frequency deviation and terminal voltage magnitude measurement. This work also assists in the microgrid design process by determining the normalized minimum storage converter sizing under a wide range of microgrid motor inertia, loading and fault clearing time with both symmetrical and asymmetrical fault types. This study evaluates the expandability of the proposed control methodologies under an unbalanced meshed microgrid with fault-induced feeder switching and multiple contingencies in addition to random power output from renewable generators. The favorable results demonstrate the robust storage converter controller performance under a dynamic changing microgrid environment.

Thermal energy storage (TES) systems play a crucial part in the success of concentrated solar power as a reliable thermal energy source. The economics and operational effectiveness of TES systems are the subjects of continuous research for improvement, in order to lower the localized cost of energy (LCOE). This study investigates the use of spherical tanks and their role in sensible heat storage in liquids. In the two tank system, typical cylindrical tanks were replaced by spherical tanks of the same volume and subjected to heat loss, stress analysis, and complete tank cost evaluation. The comparison revealed that replacing cylindrical tanks by spherical tanks in two tank molten salt storage systems could result in a 30% reduction in heat loss from the wall, with a comparable reduction in total cost. For a one tank system (or thermocline system), a parametric computational fluid dynamic (CFD) study was performed in order to obtain fluid flow parameters that govern the formation and maintenance of a thermocline in a spherical tank. The parametric study involved the following dimensionless numbers: Re (500-7500), Ar (0.5-10), Fr (0.5-3), and Ri (1-100). The results showed that within the examined range of flow characteristics, the inlet Fr number is the most influential parameter in spherical tank thermocline formation and maintenance, and the largest tank thermal efficiency in a spherical tank is achieved at Fr = 0.5. Experimental results were obtained to validate the CFD model used in the parametric study. For the flow parameters within the current model, the use of an eddy viscosity turbulence model with variable turbulence intensity delivered the best agreement with experimental results. Overall, the experimental study using a spherical one tank setup validated the results of the CFD model with acceptable accuracy.

The goal of this study was to determine the economic feasibility of battery energy storage system (BESS). Three major economic benefits derived from BESS using were studied: 1. Energy Purchase Shifting, 2. Distribution Feeder Deferral, 3. Outage Avoidance. The economic analysis was based on theoretical modeling of the BESS and distribution system. Three simulation models were developed to quantify the effects of different parameters, such as: BESS round-trip efficiency, life span, rated power, rated discharge time, marginal cost of electric energy, 24 h feeder load profile, annual load variation, feeder load growth rate and feeder length. An optimal battery charging/discharging method was presented to determine the differential cost of energy (DCE). The annual maximum DCE was calculated using stochastic probability analysis on seasonal load variation. The net present value was evaluated as the present value difference between two investments: first, the distribution feeder upgrade without BESS deferral, and second, with BESS deferral. Furthermore, the BESS’s contributions under different outage strategies were compared. It was determined that feeder length is the most significant parameter. The economics of the studied system becomes favorable when the feeder length exceeds a critical value.

There is a drive to transform the electricity industry in the UK from one based largely on fossil fuels to one based on low or zero carbon sources. The challenge of this transition, enabling a secure and sustainable electricity industry at an acceptable cost to consumers, has been dubbed the Energy Trilemma. Grid-connected electrical energy storage presents a potential solution to this challenge. However, the benefits of storage are split across different sectors of the electricity industry and there are a number of regulatory barriers preventing access to revenue streams. One accessible revenue stream is energy trading or price arbitrage. In current market conditions, arbitrage cannot provide sufficient revenue for electricity storage to cover its capital costs; however, some studies have suggested that with increased penetration of intermittent renewable power, electricity price volatility will increase enabling storage to become commercially viable through price arbitrage alone. This thesis examines the hypothesis that: Increased wind penetration leads to increased commercial opportunities for energy storage through price arbitrage. A linear programme is used to define the optimum operating strategy for a storage device, subject to the constraints of maximum storage capacity, charging and discharging rates, conversion efficiency and self-discharge. Initially, historic electricity prices from the British electricity market are used to investigate the value of storage with a low penetration of intermittent wind power. The results show that revenue is dependent on storage characteristics, with the performance of different technologies varying substantially. Furthermore, revenue is highly dependent on changes in market structure and fuel price variations from one year to the next. The thesis describes the development of a fundamental electricity price model based on the stacked merit order dispatch of thermal generation bidding to produce electricity in a competitive market centred around marginal generation costs. For peaking plant, an exponential uplift in price is applied to represent scarcity of supply. The implications of increasing wind power output are examined using projections of the location and capacity of future wind farms and spatially distributed hind cast wind speed data generated from a mesoscale atmospheric model. The analysis highlights that despite increased value being placed on storage in an energy system with a high penetration of wind power, opportunities for arbitrage are, in fact, reduced. This is a result of an oversupply of electricity on windy days suppressing peak electricity prices and reducing the daily price spread, which arbitrage exploits.

Energy storage is currently gaining considerable attention due to the current energy crisis and severe air pollution. The development of new and clean forms of energy and related storing devices is in high demanded. Dielectric capacitors, exhibiting high power density, long life and cycling life, are potential candidates for portable devices, transport vehicles and stationary energy resources applications. However, the energy density of dielectric capacitors is relatively low compared to that of traditional batteries, which inhibits their future development. In the current work, three types of dielectrics, namely antiferroelectric samarium-doped BiFeO3 (Bi1-xSmxFeO3), linear dielectric (potential antiferroelectric) BiNbO4 and incipient ferroelectric TiO2, have been investigated to develop their potential as energy storage capacitors. For the samarium-doped BiFeO3 (Bi1-xSmxFeO3) system, the effect of samarium content in the A-site (x=0.15, 0.16, 0.165 and 0.18) on the structural phase transitions and electrical properties across the Morphotropic Phase Boundary (MPB) were studied. A complex coexistence of rhombohedral R3c, orthorhombic Pbam and orthorhombic Pnma was found in the selected compositions. The R3c phase is the structure of pure BiFeO3, the Pbam phase has a PbZrO3-like antiferroelectric structure and the Pnma phase has a SmFeO3-like paraelectric structure. The presence of the PbZrO3-like antiferroelectric structure was confirmed by the observation of the 14{110}, 14{001}, 12{011} and 12{111} superlattice reflections in the transmission electron microscopy diffraction patterns. The weight fractions of the three phases varied with different calcination conditions and Sm substitution level. By increasing the calcination temperature, the weight fractions of the Pbam increased, while that of the R3c decreased. The fraction of the Pnma phase is mainly derived by the Sm concentration and is barely affected by the calcination temperature. The increase of Sm concentration, determined an increase of the weight fraction of the Pnma phase and a decrease of the Pbam and the R3c phases. Temperature dependent dielectric measurements and high temperature XRD of Bi0.85Sm0.15FeO3 revealed several phase transitions. The drastic weight fraction change between the Pbam and the Pnma phase around 200 °C is assumed as the Curie transition of the antiferroelectric Pbam phase. The transition at 575 °C is related to the diminishing of the R3c phase and is suggested as the Curie transition of the ferroelectric R3c phase. The Curie point of the antiferroelectric Pbam phase and the ferroelectric R3c phase in the Bi1-xSmxFeO3 ceramics shifted towards lower temperature with an increase of the Sm concentration. Current peaks were obtained in current-electric field loops in Bi0.85Sm0.15FeO3, which are correlated to domain switching in the R3c phase. The ferroelectric behavior was suppressed in Bi1-xSmxFeO3 (x=0.16, 0.165, 0.18), which is due to the gradually diminished contribution from the R3c phase. The system Bi0.82Sm0.18FeO3 showed the highest energy density of 0.64 J cm-3 (error bar ±0.02). For the BiNbO4 system, single phase α-BiNbO4 (space group Pnna) and β-BiNbO4 (space group P-1) powder and ceramics were produced. The longstanding issue related to the sequence of the temperature-induced phase transitions has been clarified. It is demonstrated that the β phase powder could be converted back to the  phase when annealed in the temperature range 800 °C -1000 °C with certain incubation time. The β to  phase transition is a slow kinetic process because sufficient temperature and time are required for the transition. In bulk ceramics with β phase, this transformation is impeded by inner stress, while it is favored by graphite-induced reducing atmosphere. A high temperature  phase has been revealed and the structure has been resolved. The structure of the  phase is monoclinic with a space group of P21/c. The lattice parameters are: a = 7.7951(1) Å, b = 5.64993(9) Å, c = 7.9048(1) Å,  = 104.691(2) Z=4. The volume is 336.76 (2) Å3. The calculated density is 7.217 g cm-3. The phase relationships among ,  and  phases have been clarified. It was found that the  phase (for both powder and ceramic) transforms into the  phase at 1040 °C on heating, and that the  phase always transforms into the  phase at 1000 °C on cooling. Meanwhile, a reversible first-order  to  phase transition is observed at ca. 1000 °C for both powder and ceramic if no incubation is processed on heating. The electric properties of both α- and - BiNbO4 have been investigated. The breakdown field of both ceramics were too low to observe any possible field-induced transition. As a result, linear P-E loops were obtained in each phase. The energy densities of α- and - BiNbO4 ceramics are 0.03 and 0.04 J cm-3 (error bar ±0.001), respectively. For the TiO2 system, ceramics were produced by conventional sintering and spark plasma sintering (SPS). Compared to conventional sintering, SPS technique produced dense ceramics without using sintering aids and avoided abnormal grain growth. Relaxation behavior related to the oxygen hopping among vacant sites is observed in the temperature range of 200 to 600 °C. TiO2 exhibits ultra-low loss at terahertz frequencies due to the reduced contribution of oxygen vacancies relaxation. TiO2 has a high breakdown field, but still has low polarization. The highest energy density obtained inTiO2 ceramics is 0.3 J cm-3 (error bar ±0.01).

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Bibliography: leaves 218-223. / by Paul Alan Basore. / M.S.

As the cost of solar energy continues to drop, the major hurdle limiting the widespread use of intermittent renewable solar energy is the lack of efficient and cost-effective energy storage. Electrochemical technologies, such as electrolyzers, photoelectrochemical cells, and fuel cells, have the potential to compensate for solar energy intermittency on a large scale, by converting excess solar energy into storable solar fuels, such as hydrogen (H2), which can be converted back to electrical energy at a later time. However, improvements in the efficiency and lifetime of these technologies, in particular the electrocatalysts, are necessary for their commercialization. During operation, efficiency losses result from energetic penalties (overpotentials) associated with several processes occurring at or near the electrocatalyst/electrolyte (ohmic resistance, kinetic barriers, and mass transport limitations). These losses can be further exacerbated due to electrocatalyst durability issues such as dissolution, agglomeration, detachment, and poisoning. A major challenge in electrocatalysis field is developing methods to mitigate these losses without adversely affecting the electrocatalytic stability, selectivity, and/or activity. One promising solution is an oxide-encapsulated electrocatalyst architecture, which has been shown to improve electrocatalyst durability and provide mechanisms for controlling reaction pathways. Previous studies on oxide-encapsulated electrocatalysts, in which metal catalysts are fully or partially covered by ultrathin layers of permeable oxide films, have mostly focused on supported nanoparticles because of their high electrochemically active surface area per catalyst loading. However, these nanoparticle-based architectures tend to have poorly defined and/or non-uniform structures which make it difficult to understand and elucidate structure-property-relationships. This dissertation investigates well-defined oxide-coated electrocatalysts, which serve as model platforms for gaining a fundamental understanding of kinetic and transport phenomena that underlie their operation. This dissertation presents three studies which highlight the versatile functionalities of oxide-encapsulated electrocatalysts to improve the electrocatalyst stability, selectivity, and activity in different electrochemical systems. This dissertation demonstrates the ability of room temperature synthesized silicon oxide (SiOx)-encapsulated Pt electrocatalysts to: i) stabilize nanoparticles and improve electron transfer, ii) mitigate catalyst poisoning and control reaction pathways through selective transport, and iii) alter reaction energetics associated with catalysis at the buried interface. First, this dissertation establishes the ability of room temperature synthesized SiOx coatings to stabilize nanoparticle electrocatalysts by mitigating electrocatalyst migration, coalescence, and detachment on metal-insulator-semiconductor (MIS) photoelectrodes for solar-driven water splitting. Metallic Pt nanoparticles are inherently unstable on the insulating support due to poor physical adhesion and electronic coupling between Pt and SiO2. To overcome this issue, a room temperature UV ozone synthesis process was used to deposit 2-10 nm thick SiOx overlayers on top of electrodeposited Pt nanoparticles to stabilize Pt on the electrode surface. The photoelectrodes containing oxide-encapsulated electrocatalysts exhibit superior durability and electron transfer (ohmic) properties compared to the photoelectrode that lacked the SiOx encapsulation. While this study demonstrates that the oxide-encapsulated electrocatalyst architecture improves the stability of electrocatalytic nanoparticles deposited on insulating materials, it does not elucidate how reactants and products transport through the SiOx barrier to reach the Pt surface. In order to gain a better understanding of kinetic and transport phenomena that govern performance of oxide-encapsulated electrocatalysts, the following studies investigate model electrodes consisting of continuous SiOx overlayers of uniform thickness deposited onto smooth Pt thin films. This planar electrode geometry allows for simple and unambiguous characterization of structure-property relationships. The next study systematically evaluates the influence of SiOx thickness on the HER performance to understand species transport through SiOx. Through detailed characterization and electroanalytical tests, it is shown that proton and H2 transport occur primarily through the SiOx coating such that the HER occurs at the buried Pt|SiOx interface. Importantly, the SiOx nanomembranes were found to exhibit high selectivity for proton and H2 transport compared to Cu2+, a model HER poison. Leveraging this property, it is shown that SiOx–encapsulation can enable poison-resistant operation of Pt HER electrocatalysts. This oxide-encapsulated architecture offers a promising approach to enhancing electrocatalyst stability while incorporating advanced catalytic functionalities such as poison resistance or tunable reaction selectivity. The final study demonstrates ability of SiOx overlayers to alter reaction energetics associated with catalysis at the buried interface. Carbon monoxide (CO), methanol, and ethanol oxidation reactions are studied for their relevance in direct alcohol fuel cell applications. Oxide-supported catalysts have been shown to enhance alcohol oxidation by promoting CO oxidation at metal/oxide interfacial regions through the so-called bifunctional mechanism, in which hydroxyls on the oxide facilitate the removal of adsorbed CO−intermediates from active sites. A key advantage of the oxide-encapsulated electrocatalyst design compared to oxide–supported nanoparticles is that the former maximizes the density of metal/oxide interfacial sites. This study shows that the SiOx overlayer provides proximal hydroxyls, in the form of silanol groups, which can enhance CO and alcohol oxidation through unique interactions at the buried Pt|SiOx interface. Overall, this dissertation highlights the potential of using oxide-encapsulated electrocatalysts for stable, selective, and efficient electrochemical production and use of solar fuels.