Li-ion batteries have become the more dominant battery type used in portable electronic devices such as cell phones, computers and more recently their application in full electric vehicles (EV). Li-ion batteries have many advantages over the traditional rechargeable systems (Pb-acid and Ni-MH) such as their higher energy density, low self-discharge, long capacity cycle life and relatively maintenance free. Due to their commercial advantages, a lot of research is done in developing new novel Li-ion electrode materials, improving existing ones and to reduce manufacturing costs in order to make them more cost effective in their applications. This study looked at the cathode material chemistry that has a typical spinel manganese oxide (LiMn2O4) type structure. For comparison the study also considered the influence of doping the phase with various metals such as Al, Mg, Co and Ni that were made as precursors using various carboxylic acids (Citric, Ascorbic, Succinic and Poly-acrylic acid) from a sol-gel process. Traditional batch methods of synthesizing the electrode material is costly and do not necessarily provide optimized electrochemical performance. Alternative continuous less energy intensive methods would help reduce the costs of the preparation of the electrode materials. This study investigated the influence of two synthesis techniques on the materials physical and electrochemical characteristics. These synthesis methods included the use of a typical batch sol-gel method and the continuous spray-drying technique. The spinel materials were prepared and characterized by Powder X-Ray Diffraction (PXRD) to confirm the formation of various phases during the synthesis process. In addition, in-situ PXRD techniques were used to track the phase changes that occurred in the typical batch synthesis process from a sol-gel mixture to the final crystalline spinel oxide. The materials were also characterized by thermal gravimetric analysis (TGA), whereby the materials decomposition mechanisms were observed as the precursor was gradually heated to the final oxide. These synthesized materials prepared under various conditions were then used to build suitable Li-ion coin type of cells, whereby their electrochemical properties were tested by simple capacity tests and electrochemical impedance spectroscopy (EIS). EIS measurements were done on the built cells with the various materials at various charge voltages. TG analysis showed that the materials underwent multiple decomposition steps upon heating for the doped lithium manganese oxides, whereas the undoped oxide showed only a single decomposition step. The results showed that all the materials achieved their weight loss below 400 °C, and that the final spinel oxide had already formed. The in-situ PXRD analysis showed the progression of the phase transitions where certain of the materials changed from a crystalline precursor to an amorphous intermediate phase and then finally to the spinel cathode oxide (Li1.03Mg0.2Mn1.77O4, and LiCo1.09Mn0.91O4). For other materials, the precursor would start as an amorphous phase, and then upon heating, convert into an impure intermediate phase (Mn2O3) before forming the final spinel oxide (Li1.03Mn1.97O4 and LiNi0.5Mn1.5O4). The in-situ study also showed the increases in the materials respective lattice parameters of the crystalline unit cells upon heating and the significant increases in their crystallite sizes when heated above 600 °C. Hence the results implied that a type of sintering of the particles would occur at temperatures above 600 °C, thereby increasing the respective crystallite size. The study showed that the cathode active materials made by the sol-gel spray-drying method would give a material that had a significantly larger surface area and a smaller crystallite size when compared to the materials made by the batch process. The electrochemical analysis showed that there was only a slight increase in the discharge capacities of the cells made with the spray-drying technique when compared to the cells made with the materials from the batch sol-gel technique. Whereas, the EIS study showed that there were distinct differences in the charging behavior of the cells made with the various materials using different synthesis techniques. The EIS results showed that there was a general decrease in the cells charge transfer resistance (Rct) as the charge potential increased regardless of the synthesis method used for the various materials. The results also showed that the lithium-ion diffusion coefficient (DLi) obtained from EIS measurements were in most of the samples higher for the cathode materials that had a larger surface area. This implied that the Li-ion could diffuse at a faster rate through the bulk material. The study concluded that by optimizing the synthesis process in terms of the careful control of the thermal parameters, the Li-ion batteries‟ cathode active material of the manganese spinel type could be optimized and be manufactured by using a continuous flow micro spray process.

Lithium-ion batteries (LIBs) play a significant role in our highly electrified world and will continue to lead technology innovations. Millions of vehicles are equipped with or directly powered by LIBs, mitigating environmental pollution and reducing energy use. This rapidly increasing use of LIBs in vehicles will introduce a large quantity of spent LIBs within an 8- to10-year span and proper handling of end-of-life (EOL) vehicle LIBs is required. Over the last several years, the Worcester Polytechnic Institute (WPI) team in the Department of Mechanical Engineering has developed a closed-loop lithium ion battery recycling process and it has been demonstrated that the recovered NMC 111 has similar or better electrochemical properties than the commercial control powder with both coin cells and pouch cells, which have been independently tested by A123 Systems and Argonne National Laboratory. In addition, the different chemical compositions of the incoming recycling streams were shown to have little observed effects on the recovered precursor and resultant cathode material. Therefore, the WPI-developed process applies to different spent Li-ion battery waste streams and is, therefore, general. During the last few years, industry has the tendency to employ higher-nickel and lower-cobalt cathode material since it can provide higher capacity and energy density and lower cost. However, higher-nickel cathode material has the intrinsic unstable properties and surface modifications can be applied to slow down its degradation. Here, two facile scalable Al2O3 coating methods (dry coating and wet coating) were applied to recycled NMC 622 and the resultants were systematically studied. The Al-rich layer from the dry coating process imparted improved structural and thermal stability in accelerated cycling performed at 45 °C between 3.0 and 4.3 V, and the capacity retention of pouch cells with dry coated NMC 622 (D-NMC) cathode increased from 83% to 91% compared to Al-free NMC 622 after 300 cycles. However, for wet coated NMC 622 (W-NMC), the increased surface area accompanying by formation of NiO rock-salt like structure could have negative impacts on the cycling performance. There exist three challenges for current LIBs’ recycling research. First of all, most of the research is done in lab-scale and the scale-up ability needs to be proven. The scale-up ability of our recycling process has been verified by our scale-up experiments. The second challenge resides in the flexibility, here once again, with our intentionally designed experiments that having various incoming chemistries, the flexibility is validated. The last challenge is the lack of reliable testing because most of the testing is conducted with coin cells. Coin cells are relatively simple format and lacks persuasion. Here, with various industrial-level cell formats that ranging from coin cell, single layer pouch cell, 1Ah cell and 11Ah cell, a reliable and trustworthy testing is established. With this validation, the hesitation of recruiting recycled materials into industry shouldn’t exist.

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The aim of this thesis is to develop a better understanding about the degradation mechanisms occurring within lithium-ion cells which eventually lead to their failure. An introduction to the components and operation of Li-ion cells is followed by proposed degradation mechanisms which limit the lifetime of cells. These mechanisms and how they can be identified from electrochemical testing are discussed. Electrolyte additives can be used to improve the safety of Li-ion cells or decrease the rate of cell degradation. Different types of additives and testing methods are discussed followed by an introduction to high precision coulometry which can be used to detect the impact of additives on cycling performance. The High Precision Charger that was constructed for this project is described and shown to meet the desired precision. The use of additives and different materials to extend lifetime of cells is shown to be detectable through the use of high precision coulometry. High precision coulometry proves to be a more efficient way of estimating the lifetime of cells under realistic conditions in a reasonably short amount of time. / MSc. Thesis

In order for battery manufacturers to have a sustainable business, the batteries they produce must be as safe as possible. For lithium-ion batteries, reducing the flammability of the electrolyte is considered to be one way to improve safety, which might be achieved by adding flame retardants to the electrolyte. On the other hand, sodium-ion batteries are attracting attention from academic researchers due to the abundance of sodium reserves compared to lithium reserves. However, there are virtually no studies about the safety of sodium-ion batteries. In this thesis, studies of these two issues will be reported. The reactivity of charged/discharged electrode materials for sodium-ion batteries in different solvents and electrolytes at elevated temperature was studied using Accelerating Rate Calorimetry (ARC). Hard carbon was studied as a negative electrode material for sodium-ion batteries. The reactivity of sodium-inserted hard carbon in solvents and electrolytes was investigated. Then, the reactivity of sodium-inserted hard carbon was compared to lithiated graphite. NaCrO2, NaxCoO2 and NaNi0.5Mn0.5O2 were studied as positive electrode materials for sodium-ion batteries. The electrochemical performance of these materials was investigated. The reactivity of charged NaCrO2, NaxCoO2 and NaNi0.5Mn0.5O2 in solvents and electrolytes was studied using ARC. Sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) was studied as an electrolyte salt for sodium-ion batteries. The electrochemical performance of hard carbon and NaCrO2 in NaTFSI/PC electrolyte was studied. The reactivity of sodium-inserted hard carbon and deintercalated NaCrO2 in NaTFSI/PC electrolyte was also investigated. Triphenyl phosphate (TPP) was studied as a flame retardant additive for lithium-ion batteries. Its impact on electrochemical performance of negative electrode materials (petroleum coke and graphite) and positive electrode materials (LiNi1/3Mn1/3Co1/3O2 (NMC) and LiNi0.8Co0.15Al0.05O2 (NCA)) was studied using an automated storage test, symmetric cells and Electrochemical Impedance Spectroscopy (EIS). The reactivity of lithiated graphite, deintercalated NMC and NCA in electrolyte containing TPP was investigated using ARC. Finally, the flammability of electrolytes containing TPP was studied using a Self-Extinguishing Time (SET) test.

Nickel-manganese-cobalt oxide (NMC) cathode materials have been applied in most Li-ion batteries, but there are nevertheless some concerns regarding the stability of this material. High voltage and high temperature during charging have been shown to accelerate the dissolution of NMC due to the release of more acidic components because of rapid electrolyte decomposition. Mn-contaminants (Mn2+) are hypothesized to diminish the diffusion coefficient of Li+ in the electrolyte attributed to the competitive interaction between Mn2+ ions and Li+ ions. With characterizations including 7Li and 1H pulsed field-gradient nuclear magnetic resonance (PFG-NMR) spectroscopy, we demonstrated the Mn (II)-contaminants effect on diffusion coefficient on Li+ dynamics. Under the influence of deliberate manganese salt-additive to the electrolyte, the coin cell shows a capacity fading and unstable charging behavior. The PFG-NMR measurements also validated our hypotheses, as the results showing that Mn-containment causes decrease ~15% in the diffusion coefficient on Li-self diffusion. The activation energy for lithium-ion transport over the temperature range of (273 K - 303 K), was not changed by the presence of the Mn-contaminant electrolyte, which indicates the Mn (II) does not affect the Li-ion transport mechanism. The relative test also includes comparisons with other contamination, such as iron contamination from stain-less steels spacers and copper contamination from the current collector. Additionally, the lithium self-diffusion coefficient was tested before and after charging using a full battery configuration. In electrolytes containing manganese contaminants, a more significant decrease in the diffusion coefficient was observed after charging. Ideally, operando experiments can be used to observe the impact of manganese ions on the SEI. By combining both types of experiments, a closer approximation to the actual application conditions of market-used batteries can be achieved. / Thesis / Master of Science (MSc) / The increasing maturity of lithium battery technology has also promoted the advancement of the electric vehicle manufacturing industry. As an excellent new energy material, the application and development of lithium batteries will be the main trend in the future. However, while improving battery capacity and energy density, lithium batteries also face many challenges. The entire thesis work discusses how electrolyte degradation at high temperatures and high voltages accelerates the dissolution of transition metal manganese ions in NMC materials. The dissolution of manganese ions into the electrolyte creates a competitive effect with lithium ions, thereby reducing the performance of lithium batteries. Here, NMR technology was used to measure the negative effect of manganese ions on the self-diffusion coefficient of lithium ions in the electrolyte. Additionally, a set of operando experiments conducted at different discharge rates demonstrated the changes in mossy lithium and the solid electrolyte interface during the charge and discharge phases caused by pulse discharge. This also proved that such experimental designs can track the impact of manganese ions on the solid electrolyte interface and test the dissolution behavior and impact of manganese ions under different charge and discharge rates.

Lithium-alloying anode materials have attracted much attention as an alternative to carbon due to their high theoretical gravimetric capacities (e.g. Li4.4Si: 4200 mAh g-1, Li4.4Sn: 990 mAh g-1, and Li3Sb: 660 mAh g-1). An additional benefit of lithium alloying metals is that some of the react at a higher potentials vs. Li/Li+ than carbon, which can mitigate safety issues caused by solid-electrolyte interface layer formation and lithium plating. One of the most promising lithium -alloying anode materials that are being pursued are Sn-based materials due to their high capacity and tap density. This thesis investigates the synthesis and characterization of Sn-based lithium-ion battery anodes. SnSb-TiC-C and FeSn2-TiC nanocomposite alloy anodes for lithium-ion batteries have been synthesized by a mechanochemical process involving high-energy mechanical milling of Ti/Sn, Ti/M (M = Fe or Sb), and C. Characterization of the nanocomposites formed with x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) reveals that these alloys are composed of crystalline nanoparticles of FeSn2 and SnSb dispersed in a matrix of TiC and carbon. The SnSb-TiC-C alloy shows an initial gravimetric capacity of 653 mAh g-1 (1384 mAh cm-3), an initial coulombic efficiency of 85%, and a tap density of 1.8 g cm-3. The FeSn2-TiC alloy shows an initial gravimetric capacity of 510 mAh g-1 (1073 mAh cm-3), an initial coulombic efficiency of 71%, and a tap density of 2.1 g cm-3. The TiC-C buffer matrix in the nanocomposite alloy anodes accommodates the large volume change occurring during the charge-discharge process and leads to good cyclability compared to pure FeSn2 and SnSb anodes. / text

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