Theses and Dissertations from UMD
Permanent URI for this communityhttp://hdl.handle.net/1903/2
New submissions to the thesis/dissertation collections are added automatically as they are received from the Graduate School. Currently, the Graduate School deposits all theses and dissertations from a given semester after the official graduation date. This means that there may be up to a 4 month delay in the appearance of a give thesis/dissertation in DRUM
More information is available at Theses and Dissertations at University of Maryland Libraries.
Browse
7 results
Search Results
Item DIRECT INK WRITING SOLID-STATE LI+ CONDUCTING CERAMICS FOR NEXT GENERATION LITHIUM METAL BATTERIES(2024) Godbey, Griffin Luh; Wachsman, Eric D; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The global pursuit of safer and higher-capacity energy storage devices emphasizes the crucial link between the microstructures of electrochemically active materials and overall battery performance. The emergence of solid-state electrolytes featuring multi-layered, variable porosity microstructures presents fresh opportunities for developing the next generation of rechargeable batteries. However, this advancement also brings forth novel challenges in terms of device integration and operation. In this dissertation, solid-state Li-ion conducting electrolytes were 3D printed to enhance the performance of porous electrolyte layers within porous-dense-porous trilayer systems.LLZO-based garnet electrolyte scaffolds were fabricated via 3D printing using direct ink writing (DIW), facilitating the generation of scaffolds with minimal tortuosity and constriction in comparison to previous porous scaffolds manufactured through tape casting. Rheological techniques, including stress and time sweep tests, were employed to characterize the DIW inks and discern their conformal and self-supporting properties. The analysis focused on ink characteristics critical for Direct Ink Writing (DIW), emphasizing properties essential for achieving high aspect ratio printing and minimal constriction in 3D structures. Drawing from this ink research, two distinct 3D architectures, columns and grids, were fabricated. Column structures were utilized in assembling Li-NMC622 and Li-SPAN cells, with detailed discussions highlighting improvements in printing and sintering outcomes. Notably, NMC622, characterized by larger particle sizes, demonstrated complete infiltration within 3D printed porous networks, yielding a promising specific capacity of 169.9 mAh/g with minimal capacity fade. Further optimization involved integrating a porous 3D scaffold to facilitate SPAN infiltration in Li-SPAN cells, resulting in a specific capacity of 1594 mAh/g, albeit with significant capacity fade. The Li-S was implemented into a grid structure achieving 763 mAh/gS with less than 0.25% capacity loss over 16 cycles. Lastly, comprehensive morphology analysis was conducted to evaluate the effectiveness of our optimal DIW structures and to inform future enhancements of such cells.Item OPTIMAL PROBING OF BATTERY CYCLES FOR MACHINE LEARNING-BASED MODEL DEVELOPMENT(2024) Nozarijouybari, Zahra; Fathy, Hosam HF; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)This dissertation examines the problems of optimizing the selection of the datasets and experiments used for parameterizing machine learning-based electrochemical battery models. The key idea is that data selection, or “probing” can empower such models to achieve greater fidelity levels. The dissertation is motivated by the potential of battery models to enable theprediction and optimization of battery performance and control strategies. The literature presents multiple battery modeling approaches, including equivalent circuit, physics-based, and machine learning models. Machine learning is particularly attractive in the battery systems domain, thanks to its flexibility and ability to model battery performance and aging dynamics. Moreover, there is a growing interest in the literature in hybrid models that combine the benefits of machine learning with either the simplicity of equivalent circuit models or the predictiveness of physics-based models or both. The focus of this dissertation is on both hybrid and purely data-driven battery models. Moreover, the overarching question guiding the dissertation is: how does the selection of the datasets and experiments used for parameterizing these models affect their fidelity and parameter identifiability? Parameter identifiability is a fundamental concept from information theory that refers to the degree to which one can accurately estimate a given model’s parameters from input-output data. There is substantial existing research in the literature on battery parameter identifiability. An important lesson from this literature is that the design of a battery experiment can affect parameter identifiability significantly. Hence, test trajectory optimization has the potential to substantially improve model parameter identifiability. The literature explores this lesson for equivalent circuit and physics-based battery models. However, there is a noticeable gap in the literature regarding identifiability analysis and optimization for both machine learning-based and hybrid battery models. To address the above gap, the dissertation makes four novel contributions to the literature. The first contribution is an extensive survey of the machine learning-based battery modeling literature, highlighting the critical need for information-rich and clean datasets for parameterizing data-driven battery models. The second contribution is a K-means clustering-based algorithm for detecting outlier patterns in experimental battery cycling data. This algorithm is used for pre-cleaning the experimental cycling datasets for laboratory-fabricated lithium-sulfur (Li-S) batteries, thereby enabling the higher-fidelity fitting of a neural network model to these datasets. The third contribution is a novel algorithm for optimizing the cycling of a lithium iron phosphate (LFP) to maximize the parameter identifiability of a hybrid model of this battery. This algorithm succeeds in improving the resulting model’s Fisher identifiability significantly in simulation. The final contribution focuses on the application of such test trajectory optimization to the experimental cycling of commercial LFP cells. This work shows that test trajectory optimization is s effective not just at improving parameter identifiability, but also at probing and uncovering higher-order battery dynamics not incorporated in the initial baseline model. Collectively, all four of these contributions show the degree to which the selection of battery cycling datasets and experiments for richness and cleanness can enable higher-fidelity data-driven and hybrid modeling, for multiple battery chemistries.Item ELECTROLYTE AND INTERFACE DESIGNATION FOR HIGH-PERFORMANCE SOLID-STATE LITHIUM METAL BATTERIES(2024) Zhang, Weiran; Wang, Chunsheng; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The demand for advanced battery technology is intensifying as electric energy becomes the foundation of modern technologies, such as smart devices, transportation, and artificial intelligence. Batteries play a crucial role in meeting our increasing energy demands and transitioning towards cleaner and more sustainable energy sources. However, range anxiety and safety concerns still hinder the widespread application of battery technology.Current Li-ion batteries, based on graphite anode, have revolutionized battery technology but are nearing the energy density limits. This necessitates the development of metal batteries, employing lithium metal as anode which eliminates host materials that do not contribute to capacity, thereby offering 10 times higher specific capacity. Recent research on lithium metal batteries has seen a significant surge, with growing knowledge transitioning from Li+ intercalation chemistry (graphite) to Li metal plating/stripping. The electrolyte, which was previously regarded as an inert material and acting as a Li+ ion transportation mediator, has gradually attracted researchers’ attention due to its significant impact on the solid electrolyte interphase (SEI) and the Li metal plating/stripping behaviors. Compared to the traditional liquid electrolytes, solid-state lithium metal batteries (SSLMB) have been regarded as the holy grail, the future of electric vehicles (EVs), due to their high safety and potential for higher energy density. However, there are notable knowledge gaps between liquid electrolytes and solid-state electrolytes (SSEs). The transition from liquid-solid contact to solid-solid contact poses new challenges to the SSLMB. As a result, the development of SSLMB is strongly hindered by interface challenges, including not only the Li/SSE interfaces and SSE/cathode interfaces but also SSE/SSE interfaces. In this dissertation, I detailed our efforts to highlight the role of electrolytes and interfaces and establish our understanding and fundamental criteria for them. Building on this understanding, we propose effective and facile engineering solutions that significantly enhance batterie metrics to meet real-world application demand. Rather than simply introducing new compositions or new designations, we are dedicated to introducing our understanding and mechanism behind it, we hope the scientific understanding, the practical solution, and the applicability to various systems can further guide and inspire the electrolyte and interface designation for next-generation battery technology.Item Assessing the Thermal Safety and Thermochemistry of Lithium Metal All-Solid-State Batteries Through Differential Scanning Calorimetry and Modeling(2023) Johnson, Nathan Brenner; Albertus, Paul; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Solid-state batteries are often considered to have superior safety compared to their liquid electrolyte counterparts, but further analysis is needed, especially because the desired higher specific energy of a solid-state lithium metal battery results in a higher potential temperature rise from the electrical energy in the cell. Safety is a multi-faceted issue that should be carefully assessed. We build "all-inclusive microcell" Differential Scanning Calorimetry samples that include all cell stack layers for a Li0.43CoO2 | Li7La3Zr2O12 | Li cell in commercially relevant material ratios (e.g. capacity matched electrodes) and gather heat flow data. From this data, we use thermodynamically calculated enthalpies of reactions for this cell chemistry to predict key points in cell thermal runaway (e.g., onset temperature, maximum temperature) and assess battery safety at the materials stage of cell development. We construct a model of the temperature rise during a thermal ramp test and short circuit in a large-format solid-state Li0.43CoO2 | Li7La3Zr2O12 | Li battery based on microcell heat flow measurements. Our model shows self-heating onset temperatures at ∼200-250°C, due to O2 released from the metal oxide cathode. Cascading exothermic reactions may drive the cell temperature during thermal runaway to ∼1000 °C in our model, comparable to temperature rise from high-energy Li-ion cells, but subject to key assumptions such as O2 reacting with Li. Higher energy density cathode materials such as LiNi0.8Co0.15Al0.05O2 in our model show peak temperatures >1300°C. Transport of O2 or Li through the solid-state separator (e.g., through cracks), and the passivation of Li metal by solid products such as Li2O, are key determinants of the peak temperature. Our work demonstrates the critical importance of the management of molten Li and O2 gas within the cell, and the importance of future modeling and experimental work to quantify the rate of the 2Li+1/2O2→Li2O reaction, and others, within a large format Li metal solid-state battery.Item INVESTIGATION OF ORDERED POROUS MATERIALS FOR LITHIUM AND MAGNESIUM IONS ELECTROCHEMICAL ENERGY STORAGE(2021) Henry, Hakeem Kimani; Lee, Sangbok; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)As portable electronics and electric vehicles become a more integral part of everyday life, rechargeable electrical energy storage devices (batteries) capable of providing greater energy and power densities will soon be necessary. Lithium-ion batteries (LIBs) have dominated this area of rechargeable energy storage devices since their commercialization in 1990. However, as electronic devices continue to advance, battery technology will have to go beyond conventional lithium-ion battery systems to power these devices. Among the many possible alternatives to lithium, magnesium is a promising candidate. In comparison to lithium, magnesium is more abundant, lower in cost, and more environmentally friendly. Magnesium batteries can also utilize a Mg metal anode which offers a high volumetric capacity and low standard reduction potential. Despite the potential benefits, Mg batteries suffer from several drawbacks. The three main issuesplaguing Mg batteries are (1) a lack of practical cathodes due to slow insertion kinetics of the divalent Mg2+ ion, (2) incompatibility between Mg electrolytes and high voltage cathodes, (3) and parasitic and passivating reactions occurring at the Mg metal anode surface. The work of this dissertation aims to address the Mg2+ insertion issue by developing modified cathodes with enhanced electrochemical performance. In the first study, the effect of structure and hydration on Mg2+ intercalation into amorphous and crystalline V2O5 films was systematically investigated by electrochemical methods. It was determined that the high water content of electrodeposited V2O5 films was the primary factor impacting Mg2+ intercalation, while the crystal structure played a secondary role. In the second study, an ordered mesoporous carbon (OMC) structure was grown on the surface of carbon nanotubes (CNT) to achieve a novel electrode architecture. The hybrid carbon structure allowed for fast ion diffusion and high electronic conductivity. The porous structure also served as an excellent host for the deposition of high-capacity cathode materials for an all-in-one electrode design. In the final study, the OMC synthesis method was paired with electrodeposited V2O5 protocol to further investigate the OMC electrochemical performance. Overall, the work of this dissertation contributes to the development and commercialization of rechargeable Mg batteries by elucidating a portion of this complex chemistry.Item Nanomaterials for Garnet Based Solid State Energy Storage(2018) Dai, Jiaqi; Hu, Liangbing; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Solid state energy storage devices with solid state electrolytes (SSEs) can potentially address Li dendrite-dominated issues, enabling the application of metallic lithium anodes to achieve high energy density with improved safety. In the past several decades, many outstanding SSE materials (including conductive oxides, phosphates, hydrides, halides, sulfides, and polymer-based composites) have been developed for solid-state batteries. Among various SSEs, garnet-type Li7La3Zr2O12 (LLZO) is one of the most important and appealing candidates for its high ionic conductivity (10-4~10-3 S/cm) at room temperature, wide voltage window (0.0-6.0V), and exceptional chemical stability against Li metal. However, its applications in current solid state energy storage devices are still facing various critical challenges. Therefore, in this quadripartite thesis I focus on developing nanomaterials and corresponding processing techniques to improve the comprehensive performance of solid state batteries from the perspectives of electrolyte design, interface engineering, cathode improvement, and full cell construction. The first part of the thesis provides two novel designs of garnet-based SSE with outstanding performance enabled by engineered nanostructures: a 3D garnet nanofiber network and a multi-level aligned garnet nanostructure. The second part of the thesis focuses on negating the anode|electrolyte interfacial impedance. It consists of several processing techniques and a comprehensive understanding, through systematic experimental analysis, of the governing factors for the interfacial impedance in solid state batteries using metallic anodes. The third part of the thesis reports several processing techniques that can raise the working voltage of Li2FeMn3O8 (LFMO) cathodes and enable the self-formation of a core-shell structure on the cathode to achieve higher ionic conductivity and better electrochemical stability. The development and characterization of a solid state energy storage device with a battery-capacitor hybrid design is included in the last part of the thesis.Item SOFT HYDROGEL BATTERIES: THE DANIELL CELL CONCEPTUALIZED IN HYBRID HYDROGELS(2015) Goyal, Ankit; Raghavan, Srinivasa R; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Energy storage devices such as batteries are important elements in many electronic devices. Currently, researchers are seeking to create new electronic devices that are "soft", i.e., bendable and stretchable. However, the batteries that power such devices are still mostly hard structures. In the current thesis, we have attempted to develop a "soft" battery out of hydrogels. Specifically, we have made a soft version of the Daniell Cell, which is a classic electrochemical cell. Our design involves a hybrid gel composed of three distinct layers. The top and bottom layers are gels swollen with a zinc salt and a copper salt, respectively, while the middle layer is akin to a "salt bridge" between the two. The hybrid gel is made by a polymerization technique developed in our laboratory and it retains good mechanical integrity (i.e., the individual layers do not delaminate). Zinc and copper foils are then attached to the hydrogel, thus creating an overall battery, and its discharge performance is reported. One unique aspect of these gel batteries is that they can be dehydrated and stored in a dry form, whereupon they are no longer batteries. In this inactive state, the materials are safe and light to transport. Upon rehydration, the gels revert to being functional batteries. This concept could be useful for military or other applications where an emergency energy storage is needed.