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Structural Studies of Degradation Mechanism of Lithium Rich Manganese, Nickel, and Iron Based Cathodes
Title
Structural Studies of Degradation Mechanism of Lithium Rich Manganese, Nickel, and Iron Based Cathodes
Creator
Aryal, Shankar
Date
2018
Description
Layered oxide compounds are superior with respect to discharge voltage and discharge specific capacity compared to other families of cathodes....
Show moreLayered oxide compounds are superior with respect to discharge voltage and discharge specific capacity compared to other families of cathodes. Therefore, LiCoO2 and LiMnxNiyCozO2, are the most commonly used cathodes since the commercialization of lithium ion battery. Recently, Li rich Ni, Mn, and Co oxide composite cathodes have been introduced with some improvements. As Co is toxic and expensive, attempts have been made to replace Co with cheap and environmentally friendly Fe. This dissertation reports that comparable discharge specific capacity and discharge voltage can be achieved by replacing Co with Fe and optimizing the composition of Mn, Ni, and Fe. However, the capacity and voltage fading on cycling are still remaining challenges. Structural change on electrochemical cycling is the main reason behind this fading. X-ray absorption spectroscopy (XAS), the specific element probe technique to study local structure and X-ray diffraction (XRD) to study the crystallographic phase information are utilized to understand the degradation/aging mechanism. A series of Li rich Mn, Ni, and Fe oxide composite cathode materials Li1.2Mn(0.30+x)Ni(0.40-x)Fe0.10O2 for x = 0, 0.05, 0.10, 0.15, 0.20 and 0.25 were prepared using a sol-gel synthesis method. Rhombohedral and monoclinic crystal phases are found in Li rich Mn, Ni, and Fe composite oxide materials, but pure rhombohedral phase cannot be obtained without excess Li in the stoichiometric LiMO2 form. The pure monoclinic phase Li2MnO3 is also synthesized to confirm its presence in the composite oxide cathodes. Particle size and surface morphology are studied with scanning electron microscopy. The composite cathodes are cycled to over 100 cycles at 0.3C, for C = 250 mAhg-1 rate. XAS before and after 100 electrochemical cycles of Li rich Mn-Ni-Fe based cathodes is reported for the first time. The determination of fractional contents of monoclinic and rhombohedral phases in the composite oxide cathodes is not possible by powder XRD analysis, however, Li2MnO3 content decreases on decreasing Mn content and on increasing Ni content. The composition with higher Ni content has a higher degree of cation mixing. The synergistic effect of rhombohedral and monoclinic phases in Li rich Mn, Ni, and Fe based cathode is critical for stable electrochemical performance. The Li1.2Mn0.50Ni0.20Fe0.10O2 cathode showed the most stable cyclability performance (194 mAhg-1 first discharge capacity with 94 % capacity retention after 100 cycles at 0.3C rate) however, Li1.2Mn0.40Ni0.30Fe0.10O2 (220 mAhg-1 first discharge capacity with 57 % capacity retention) and Li1.2Mn0.55Ni0.15Fe0.10O2 (241 mAhg-1 first discharge capacity with 68 % capacity retention) cathodes showed higher 1st discharge capacity but poor cyclability under the same charge/discharge cycling.The XAS at Mn K-edge is used to explain the mechanism of Li2MnO3 activation for the improved electrochemical performance of Li rich Mn, Ni, and Fe oxide composite cathode, however Li2MnO3 contributed differently in different compositions. Synchrotron XRD and XAS measurements probed the lattice size expansion, which decreases the chemical potential of Li ions in the cathode on cycling leading to lower discharge voltage after cycling.
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Synthesis and Processing of NaSICON Membranes with High Ionic Conductivity and Good Mechanical Strength
Title
Synthesis and Processing of NaSICON Membranes with High Ionic Conductivity and Good Mechanical Strength
Creator
Chiang, Shan-Ju
Date
2019
Description
Natrium super ion conductors (NaSICONs), Na1+xZr2SixP3-xO12 (0 ≤ x ≤ 3) are compounds that commonly used as solid electrolytes and membranes...
Show moreNatrium super ion conductors (NaSICONs), Na1+xZr2SixP3-xO12 (0 ≤ x ≤ 3) are compounds that commonly used as solid electrolytes and membranes of sodium based batteries, or in gas sensors and fuel cells due to their high sodium ion conductivity, low thermal expansion, and ability to accommodate ions in the lattice. However, NaSICON with high relative density (> 97%) and minimum impurity phases is found to be very difficult to obtain. Furthermore, the cost of the general synthesis methods is a serious drawback. Multi-high-temperature heating procedures is often employed to increase the density and to attain the single phase NaSICON because the particle size and free ZrO2 are better reduced. This research explores the possibility of densification and synthesis of NaSICON in one high-temperature reaction through a novel process termed Integrated Mechanical and Thermal Activation (IMTA) and the co-sintering behavior as well as the NaSICON composite membranes from tape casting. The sintering temperature of NaSICON was decreased by mechanical activation at room temperature using high-energy ball milling. Sintered NaSICON-based materials showed highest total ionic conductivity of 1.45 × 10-3 S cm-1 at room temperature and high density of 3.155 g cm-3 (96.5%). An alternative to obtaining full densification (99%) of NaSICON ceramics was developed utilizing traditional solid-state reaction. This sintered NaSICON without any sintering aid exhibited the total conductivity, 6.59 × 10-4 S cm-1 at 25 °C, and the highest density of 3.238 g cm-3, a better than 2.6% enhancement from the original samples.The second part of the work has comprised of successful fabrication of NaSICON/polymer composite membranes and bi-layered NaSICON/stainless steel membranes to enhance the mechanical flexibility of pure NaSICON films. The effect of different particle sizes of stainless steel on the sintering behavior and shrinkage rate were studied systematically. The effect of solid content in the slurry was also studied to control the density of both support layer and NaSICON body. The affect structural ratios have on co-sintered tapes along with ionic conductivity was investigated using Electrochemical Impedance Spectroscopy (EIS). The co-sintered membrane exhibited a total conductivity as high as 4.580 × 10-4 S/cm at room temperature. EIS results showed the high Na-ions conductivity strongly depends on the feature of grain boundary and the high densification of NaSICON layer.
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High Energy High Power Primary Lithium Batteries with Graphite Fluoride and Functionalized Boron Nitride Cathodes
Title
High Energy High Power Primary Lithium Batteries with Graphite Fluoride and Functionalized Boron Nitride Cathodes
Creator
Huo, Haobin
Date
2022
Description
The present Thesis concerns with the creation of high energy and high power batteries through the utilization of functionalized 2D materials...
Show moreThe present Thesis concerns with the creation of high energy and high power batteries through the utilization of functionalized 2D materials such as graphite fluoride (CFx) and functionalized boron nitride (FBN). The recent literature of Li-CFx batteries brings forward several methods to fabricate high energy and high power batteries. These methods include nano-architecture and porosity design, boron doping, electrolyte additives etc. The resulting batteries are capable to achieve 800-1000 Wh/kg energy density at a power density of 60-70 kW/kg. Our method is capable to achieve the same performance in a much simpler way by the application of a binder that also functions as an effective inhibitor of the growth of LiF crystals. Since LiF is the discharge product of Li-CFx batteries, it typically clogs the pores of the cathode and avoids fast discharge. Methods that increase the power density of Li-CFx batteries typically focus on the amorphization/dissolution of LiF to allow for a fast Li ion diffusion. Our solution using the effective binder appears to be well suited for a scalable production of high energy and high power Li-CFx batteries through a very small modification of existing production lines. Such high energy and high power batteries are needed for the electrification of aircraft such as unmanned aerial vehicles (UAVs), vertical take-off and landing planes (VTOLs), passenger airplanes and pulsed power sources. While Li-CFx batteries are not rechargeable this is not a problem for the above mentioned applications as current rechargeable batteries cannot provide the required energy and power densities.Li-FBN batteries may provide a rechargeable alternative to Li-CFx when fully developed. In the present thesis, we have demonstrated Li-FBN batteries with similar discharge plateaus and approximately half the capacity of Li-CFx batteries. Our Li-FBN batteries are also rechargeable to a much greater extent than Li-CFx.
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Developing Advanced Materials for Carbon Dioxide Electroreduction to Value-Added Chemicals and Fuels
Title
Developing Advanced Materials for Carbon Dioxide Electroreduction to Value-Added Chemicals and Fuels
Creator
Esmaeilirad, Mohammadreza
Date
2023
Description
Developing highly efficient electrocatalysts for the carbon dioxide reductionreaction (CO2RR) to value-added fuels and chemicals offers a...
Show moreDeveloping highly efficient electrocatalysts for the carbon dioxide reductionreaction (CO2RR) to value-added fuels and chemicals offers a feasible pathway for renewable energy storage and could help mitigate the ever-increasing carbon dioxide (CO2) emissions from human activities. Different catalysts are known to catalyze CO2RR in aqueous solutions. Most known catalysts are only capable of transferring 2 electrons with needed protons to CO2 producing either carbon monoxide (CO) or formic acid (HCOOH). Copper (Cu) is the only electrocatalytic material that converts CO2 into different types of hydrocarbon products. Additionally, owing to Cu’s natural abundance and low cost, it has been intensively studied for CO2RR for decades. However, the required high input energy (overpotential), low product selectivity towards valuable fuel products, and the lack of long-term stability remain major challenges for Cu-based catalysts. This work aims to develop new materials that produce hydrocarbons at lower overpotentials with higher rates and greater selectivity than current copper catalysts. By implementing a process referred to as the electrocatalyst discovery cycle iterations between predications, catalyst testing, and active site characterization allow for the rational design and discovery of new and improved electrocatalysts for CO2RR. This methodology led to the discovery of different heteroatomic catalysts as low overpotential catalysts for electroreduction of CO2 high energy density hydrocarbon products.
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