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Description
Vehicles powered by electricity and alternative-fuels are becoming a more popular form of transportation since they have less of an environmental impact than standard gasoline vehicles. Unfortunately, their success is currently inhibited by the sparseness of locations where the vehicles can refuel as well as the fact that many of

Vehicles powered by electricity and alternative-fuels are becoming a more popular form of transportation since they have less of an environmental impact than standard gasoline vehicles. Unfortunately, their success is currently inhibited by the sparseness of locations where the vehicles can refuel as well as the fact that many of the vehicles have a range that is less than those powered by gasoline. These factors together create a "range anxiety" in drivers, which causes the drivers to worry about the utility of alternative-fuel and electric vehicles and makes them less likely to purchase these vehicles. For the new vehicle technologies to thrive it is critical that range anxiety is minimized and performance is increased as much as possible through proper routing and scheduling. In the case of long distance trips taken by individual vehicles, the routes must be chosen such that the vehicles take the shortest routes while not running out of fuel on the trip. When many vehicles are to be routed during the day, if the refueling stations have limited capacity then care must be taken to avoid having too many vehicles arrive at the stations at any time. If the vehicles that will need to be routed in the future are unknown then this problem is stochastic. For fleets of vehicles serving scheduled operations, switching to alternative-fuels requires ensuring the schedules do not cause the vehicles to run out of fuel. This is especially problematic since the locations where the vehicles may refuel are limited due to the technology being new. This dissertation covers three related optimization problems: routing a single electric or alternative-fuel vehicle on a long distance trip, routing many electric vehicles in a network where the stations have limited capacity and the arrivals into the system are stochastic, and scheduling fleets of electric or alternative-fuel vehicles with limited locations to refuel. Different algorithms are proposed to solve each of the three problems, of which some are exact and some are heuristic. The algorithms are tested on both random data and data relating to the State of Arizona.
ContributorsAdler, Jonathan D (Author) / Mirchandani, Pitu B. (Thesis advisor) / Askin, Ronald (Committee member) / Gel, Esma (Committee member) / Xue, Guoliang (Committee member) / Zhang, Muhong (Committee member) / Arizona State University (Publisher)
Created2014
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Description
This study evaluates the potential profitability and environmental benefit available by providing renewable energy from solar- or wind-generated sources to electric vehicle drivers at public charging stations, also known as electric vehicle service equipment (EVSE), in the U.S. Past studies have shown above-average interest in renewable energy by drivers

This study evaluates the potential profitability and environmental benefit available by providing renewable energy from solar- or wind-generated sources to electric vehicle drivers at public charging stations, also known as electric vehicle service equipment (EVSE), in the U.S. Past studies have shown above-average interest in renewable energy by drivers of plug-in electric vehicles (PEVs), though no study has evaluated the profitability and environmental benefit of selling renewable energy to PEV drivers at public EVSE. Through an online survey of 203 U.S.-wide PEV owners and lessees, information was collected on (1) current PEV and EVSE usage, (2) potential willingness to pay (WTP) for upgrading their charge event to renewable energy, and (3) usage of public EVSE if renewable energy was offered. The choice experiment survey method was used to avoid bias known to occur when directly asking for WTP. Sixty percent of the participants purchased their PEVs due to environmental concerns. The survey results indicate a 506% increase in the usage of public pay-per-use EVSE if renewable energy was offered and a mean WTP to upgrade to renewable energy of $0.61 per hour for alternating current (AC) Level 2 EVSE and $1.82 for Direct Current (DC) Fast Chargers (DCFC). Based on data from the 2013 second quarter (2Q) report of The EV Project, which uses the Blink public EVSE network, this usage translates directly to an annual gross income increase of 668% from the original $1.45 million to $11.1 million. Blink would see an annual cost of $16,005 per year for the acquisition of the required renewable energy as renewable energy credits (RECs). Excluding any profit seen purely from the raise in usage, $3.8 million in profits would be gained directly from the sale of renewable energy. Relative to a gasoline-powered internal combustion engine passenger vehicle, greenhouse gas (GHG) emissions are 42% less for the U.S. average blend grid electricity-powered electric vehicle and 99.997% less when wind energy is used. Powering all Blink network charge events with wind energy would reduce the annualized 2Q 2013 GHG emissions of 1,589 metric tons CO2 / yr to 125 kg CO2 / yr, which is the equivalent of removing 334 average U.S. gasoline passenger cars from the road. At the increased usage, 8,031 metric tons CO2 / yr would be prevented per year or the equivalent of the elimination of 1,691 average U.S. passenger cars. These economic and environmental benefits will increase as PEV ownership increases over time.
ContributorsNienhueser, Ian Andrew (Author) / Qiu, Yueming (Thesis advisor) / Rogers, Bradley (Thesis advisor) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Commercial Li-ion cells (18650: Li4Ti5O12 anodes and LiCoO2 cathodes) were subjected to simulated Electric Vehicle (EV) conditions using various driving patterns such as aggressive driving, highway driving, air conditioning load, and normal city driving. The particular drive schedules originated from the Environment Protection Agency (EPA), including the SC-03, UDDS, HWFET,

Commercial Li-ion cells (18650: Li4Ti5O12 anodes and LiCoO2 cathodes) were subjected to simulated Electric Vehicle (EV) conditions using various driving patterns such as aggressive driving, highway driving, air conditioning load, and normal city driving. The particular drive schedules originated from the Environment Protection Agency (EPA), including the SC-03, UDDS, HWFET, US-06 drive schedules, respectively. These drive schedules have been combined into a custom drive cycle, named the AZ-01 drive schedule, designed to simulate a typical commute in the state of Arizona. The battery cell cycling is conducted at various temperature settings (0, 25, 40, and 50 °C). At 50 °C, under the AZ-01 drive schedule, a severe inflammation was observed in the cells that led to cell failure. Capacity fading under AZ-01 drive schedule at 0 °C per 100 cycles is found to be 2%. At 40 °C, 3% capacity fading is observed per 100 cycles under the AZ-01 drive schedule. Modeling and prediction of discharge rate capability of batteries is done using Electrochemical Impedance Spectroscopy (EIS). High-frequency resistance values (HFR) increased with cycling under the AZ-01 drive schedule at 40 °C and 0 °C. The research goal for this thesis is to provide performance analysis and life cycle data for Li4Ti5O12 (Lithium Titanite) battery cells in simulated Arizona conditions. Future work involves an evaluation of second-life opportunities for cells that have met end-of-life criteria in EV applications.
ContributorsAbdelhay, Reem (Author) / Kannan, Arunachala Mada (Thesis advisor) / Wishart, Jeffrey (Committee member) / Nam, Changho (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The most important metrics considered for electric vehicles are power density, efficiency, and reliability of the powertrain modules. The powertrain comprises of an Electric Machine (EM), power electronic converters, an Energy Management System (EMS), and an Energy Storage System (ESS). The power electronic converters are used to couple the motor

The most important metrics considered for electric vehicles are power density, efficiency, and reliability of the powertrain modules. The powertrain comprises of an Electric Machine (EM), power electronic converters, an Energy Management System (EMS), and an Energy Storage System (ESS). The power electronic converters are used to couple the motor with the battery stack. Including a DC/DC converter in the powertrain module is favored as it adds an additional degree of freedom to achieve flexibility in optimizing the battery module and inverter independently. However, it is essential that the converter is rated for high peak power and can maintain high efficiency while operating over a wide range of load conditions to not compromise on system efficiency. Additionally, the converter must strictly adhere to all automotive standards.

Currently, several hard-switching topologies have been employed such as conventional boost DC/DC, interleaved step-up DC/DC, and full-bridge DC/DC converter. These converters face respective limitations in achieving high step-up conversion ratio, size and weight issues, or high component count. In this work, a bi-directional synchronous boost DC/DC converter with easy interleaving capability is proposed with a novel ZVT mechanism. This converter steps up the EV battery voltage of 200V-300V to a wide range of variable output voltages ranging from 310V-800V. High power density and efficiency are achieved through high switching frequency of 250kHz for each phase with effective frequency doubling through interleaving. Also, use of wide bandgap high voltage SiC switches allows high efficiency operation even at high temperatures.

Comprehensive analysis, design details and extensive simulation results are presented. Incorporating ZVT branch with adaptive time delay results in converter efficiency close to 98%. Experimental results from a 2.5kW hardware prototype validate the performance of the proposed approach. A peak efficiency of 98.17% has been observed in hardware in the boost or motoring mode.
ContributorsMullangi Chenchu, Hemanth (Author) / Ayyanar, Raja (Thesis advisor) / Qin, Jiangchao (Committee member) / Lei, Qin (Committee member) / Arizona State University (Publisher)
Created2018
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Description
There was a growing trend in the automotive market on the adoption of Hybrid Electric Vehicles (HEVs) for consumers to purchase. This was partially due to external pressures such as the effects of global warming, cost of petroleum, governmental regulations, and popularity of the vehicle type. HEV technology

There was a growing trend in the automotive market on the adoption of Hybrid Electric Vehicles (HEVs) for consumers to purchase. This was partially due to external pressures such as the effects of global warming, cost of petroleum, governmental regulations, and popularity of the vehicle type. HEV technology relied on a variety of factors which included the powertrain (PT) of the system, external driving conditions, and the type of driving pattern being driven. The core foundation for HEVs depended heavily on the battery pack and chemistry being adopted for the vehicle performance and operations. This paper focused on the effects of hot and arid temperatures on the performance of LiFePO4 (LFP) battery packs and presented a possible modeling method for overall performance.

Lithium-ion battery (LIB) packs were subjected to room and high temperature settings while being cycled under a current profile created from a drive cycle. The Federal Urban Driving Schedule (FUDS) was selected and modified to simulate normal city driving situation using an electric only drive mode. Capacity and impedance fade of the LIB packs were monitored over the lifetime of the pack to determine the overall performance through the variables of energy and power fade. Regression analysis was done on the energy and power fade of the LIB pack to determine the duration life of LIB packs for HEV applications. This was done by comparing energy and power fade with the average lifetime mileage of a vehicle.

The collected capacity and impedance data was used to create an electrical equivalent model (EEM). The model was produced through the process of a modified Randles circuit and the creation of the inverse constant phase element (ICPE). Results indicated the model had a potential for high fidelity as long as a sufficient amount of data was gathered. X-ray powder diffraction (XRD) and a scanning electron microscope (SEM) was performed on a fresh and cycled LFP battery. SEM results suggested a dramatic growth on LFP crystals with a reduction in carbon coating after cycling. XRD effects showed a slight uniformed strain and decrease in size of LFP olivine crystals after cycling.
ContributorsOpitz, Andrew (Author) / Kannan, Arunachala (Thesis advisor) / Mayyas, Abdel (Committee member) / Nam, Changho (Committee member) / Arizona State University (Publisher)
Created2016
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Description

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the rapid adoption of electric vehicles; sales of electric vehicles in 2020 are more than double what they were only a year prior. With such staggering growth it is important to understand how lithium is sourced and what that means for the environment. Will production even be capable of meeting the demand as more industries make use of this valuable element? How will the environmental impact of lithium affect growth? This thesis attempts to answer these questions as the world looks to a decade of rapid growth for lithium ion batteries.

ContributorsMelton, John (Author) / Brian, Jennifer (Thesis director) / Karwat, Darshawn (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
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Description
Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from

Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from kerogen may have implications for research focused on the Li-isotopes of buried sediments (e.g., evaluating paleoclimate variations using marine carbonates).The objective of this work is to better understand the role of kerogen in the Li geochemical cycle. The research approach consisted of 1) developing reference materials and methodologies to measure the Li-contents and δ7Li of kerogen in-situ by Secondary Ion Mass Spectrometry, 2) surveying the Li-contents and δ7Li of kerogen bearing rocks from different depositional and diagenetic environments and 3) quantifying the Li-content and δ7Li variations in kerogen empirically in a field study and 4) experimentally through hydrous pyrolysis. A survey of δ7Li of coals from depositional basins across the USA showed that thermally immature coals have light δ7Li values (–20 to – 10‰) compared to typical terrestrial materials (> –10‰) and the δ7Li of coal increases with burial temperature suggesting that 6Li is preferentially released from kerogen to porefluids during hydrocarbon generation. A field study was conducted on two Cretaceous coal seams in Colorado (USA) intruded by dikes (mafic and felsic) creating a temperature gradient from the intrusives into the country rock. Results showed that δ7Li values of the unmetamorphosed vitrinite macerals were up to 37‰ lighter than vitrinite macerals and coke within the contact metamorphosed coal. To understand the significance of Li derived from kerogen during burial diagenesis, hydrous pyrolysis experiments of three coals were conducted. Results showed that Li is released from kerogen during hydrocarbon generation and could increase sedimentary porefluid Li-contents up to ~100 mg/L. The δ7Li of coals becomes heavier with increased temperature except where authigenic silicates may compete for the released Li. These results indicate that kerogen is a significant source of isotopically light Li to diagenetic fluids and is an important contributor to the global geochemical cycle.
ContributorsTeichert, Zebadiah (Author) / Williams, Lynda B. (Thesis advisor) / Bose, Maitrayee (Thesis advisor) / Hervig, Richard (Committee member) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Lithium titanium oxide (LTO), is a crystalline (spinel) anode material that has recently been considered as an alternative to carbon anodes in conventional lithium-ion batteries (LIB), mainly due to the inherent safety and durability of this material. In this paper commercial LTO anode 18650 cells with lithium cobalt oxide (LCO)

Lithium titanium oxide (LTO), is a crystalline (spinel) anode material that has recently been considered as an alternative to carbon anodes in conventional lithium-ion batteries (LIB), mainly due to the inherent safety and durability of this material. In this paper commercial LTO anode 18650 cells with lithium cobalt oxide (LCO) cathodes have been cycled to simulate EV operating condition (temperature and drive profiles) in Arizona. The capacity fade of battery packs (pack #1 and pack#2), each consisting 6 such cells in parallel was studied. While capacity fades faster at the higher temperature (40°C), fading is significantly reduced at the lower temperature limit (0°C). Non-invasive techniques such as Electrochemical Impedance Spectroscopy (EIS) show a steady increase in the high-frequency resistance along with capacity fade indicating Loss of Active Material (LAM) and formation of co-intercalation products like Solid Electrolyte Interface (SEI). A two-stage capacity fade can be observed as previously reported and can be proved by differential voltage curves. The first stage is gradual and marks the slow degradation of the anode while the second stage is marked by a drastic capacity fade and can be attributed to the fading cathode. After an effective capacity fading of ~20%, the battery packs were disassembled, sorted and repackaged into smaller packs of 3 cells each for second-life testing. No major changes were seen in the crystal structure of LTO, establishing its electrochemical stability. However, the poor built of the 18650-cell appears to have resulted in failures like gradual electrolytic decomposition causing prominent swelling and failure in a few cells and LAM from the cathode along with cation dissolution. This result is important to understand how LTO batteries fail to better utilize the batteries for specific secondary-life applications.
ContributorsWadikar, Harshwardhan (Author) / Crozier, Peter (Thesis advisor) / Wang, Qing H (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction

Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction (SSR) from oxide precursors, requiring high reaction temperatures (900-1000 °C) and producing powder with large particle sizes, necessitating high energy milling to improve sinterability. In this dissertation, two classes of advanced synthesis methods – sol-gel polymer-combustion and molten salt synthesis (MSS) – are employed to obtain LLZO submicron powders at lower temperatures. In the first case, nanopowders of LLZO are obtained in a few hours at 700 °C via a novel polymer combustion process, which can be sintered to dense electrolytes possessing ionic conductivity up to 0.67 mS cm-1 at room temperature. However, the limited throughput of this combustion process motivated the use of molten salt synthesis, wherein a salt mixture is used as a high temperature solvent, allowing faster interdiffusion of atomic species than solid-state reactions. A eutectic mixture of LiCl-KCl allows formation of submicrometer undoped, Al-doped, Ga-doped, and Ta-doped LLZO at 900 °C in 4 h, with total ionic conductivities between 0.23-0.46 mS cm-1. By using a highly basic molten salt medium, Ta-doped LLZO (LLZTO) can be obtained at temperatures as low as 550 °C, with an ionic conductivity of 0.61 mS cm-1. The formation temperature can be further reduced by using Ta-doped, La-excess pyrochlore-type lanthanum zirconate (La2Zr2O7, LZO) as a quasi-single-source precursor, which convert to LLZTO as low as 400 °C upon addition of a Li-source. Further, doped pyrochlores can be blended with a Li-source and directly sintered to a relative density up to 94.7% with high conductivity (0.53 mS cm-1). Finally, a propensity for compositional variation in LLZTO powders and sintered ceramics was observed and for the first time explored in detail. By comparing LLZTO obtained from combustion, MSS, and SSR, a correlation between increased elemental inhomogeneity and reduced ionic conductivity is observed. Implications for garnet-based solid-state batteries and strategies to mitigate elemental inhomogeneity are discussed.
ContributorsWeller, Jon Mark (Author) / Chan, Candace K (Thesis advisor) / Crozier, Peter (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021
Description
Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si,

Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which Tetrel elements form a cage framework and encapsulate metal guest atoms. These structures can form with defects such as framework/guest atom substitutions and vacancies which result in a wide design space for tuning materials properties. The goal of this work is to establish structure property relationships within the context of Li-ion battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their electrochemical reactions with Li and show high capacities indicative of alloying reactions. DFT calculations show that Li insertion into the framework vacancies is favorable, but the migration barriers are too high for room temperature diffusion. Then, guest free type I clathrates are investigated for their Li and Na migration barriers. The results show that Li migration in the clathrate frameworks have low energy barriers (0.1- 0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g), low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray measurements and pair distribution function (PDF) analysis are used to investigate the lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results show that the Ba-clathrates undergo amorphous phase transformations which is distinct from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways. Based on the high capacities and solid-solution reaction mechanism, guest-filled clathrates could be promising precursors to form alloying anodes with novel electrochemical properties. Finally, several high temperature (300-550 °C) electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a cell using a Na β’’-alumina solid electrolyte.
ContributorsDopilka, Andrew (Author) / Chan, Candace K (Thesis advisor) / Zhuang, Houlong (Committee member) / Peng, Xihong (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021