Department of Chemistry / As an alternative energy source, lithium ion batteries have become increasingly important with a wide range of applications in industry, and many international companies are investing in this big project. This study was aimed at the development of safer lithium-ion power sources by using new organic additives to overcome the possible safety problems. In this study, the conformations and energies of several synthesized boronates were investigated through computational study using density functional theory (DFT) with the Becke’s three-parameter hybrid method utilizing the Lee-Young-Parr correlation functional (B3LYP). After initial energy optimization using Møller-Plesset Perturbation theory (MP2), the conformational preferences and energetics in vacuo were investigated using DFT calculations and the 6-31G(d,p) basis set. Subsequently, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the compounds in terms of their usefulness as electrolyte additives. At least two of these show excellent promise for use in lithium-ion batteries.

Indiana University-Purdue University Indianapolis (IUPUI) / In recent years Lithium-Ion battery as an alternate energy source has gathered lot of importance in all forms of energy requiring applications. Due to its overwhelming benefits over a few disadvantages Lithium Ion is more sought of than any other Battery types. Any battery pack alone cannot perform or achieve its maximum capacity unless there is some robust, efficient and advanced controls developed around it. This control strategy is called Battery Management System or BMS. Most BMS performs the following activity if not all Battery Health Monitoring, Temperature Monitoring, Regeneration Tactics, Discharge Profiles, History logging, etc. One of the major key contributor in a better BMS design and subsequently maintaining a better battery performance and EUL is Regeneration Tactics. In this work, emphasis is laid on understanding the prevalent methods of regeneration and designing a new strategy that better suits the battery performance. A performance index is chosen which aims at minimizing the effort of regeneration along with a minimum deviation from the rated maximum thresholds for cell temperature and regeneration current. Tuning capability is provided for both temperature deviation and current deviation so that it can be tuned based on requirement and battery chemistry and parameters. To solve the optimization problem, Pontryagin's principle is used which is very effective for constraint optimization with both state and input constraints. Simulation results with different sets of tuning shows that the proposed method has a lot of potential and is capable of introducing a new dynamic regeneration tactic for Lithium Ion cells. With the current optimistic results from this work, it is strongly recommended to bring in more battery constraints into the optimization boundary to better understand and incorporate battery chemistry into the regeneration process.

The experimental data and results demonstrated here illustrate the preparation and application of mesoporous metal oxides in energy storage, adsorption, and catalysis. First, a new method of controlling the pore size and wall thickness of mesoporous silica was developed by controlling the calcination temperature. A series of such silica were used as hard templates to prepare the mesoporous metal oxide Co₃O₄. Using other methods, such as varying the silica template hydrothermal treatment temperature, using colloid silica, varying the materials ratio etc., a series of mesoporous β-MnO₂ with different pore size and wall thickness were prepared. By using these materials it has been possible to explore the influence of pore size and wall thickness on the rate of lithium intercalation into mesoporous electrode. There is intense interest in lithium intercalation into titanates due to their potential advantages (safety, rate) replacing graphite for new generation Li-ion battery. After the preparation of an ordered 3D mesoporous anatase the lithium intercalation as anode material has been investigated. To the best of our knowledge, there are no reports of ordered crystalline mesoporous metal oxides with microporous walls. Here, for the first time, the preparation and characterization of three dimensional ordered crystalline mesoporous α-MnO₂ with microporous wall was described, in which K+ and KIT-6 mesoporous silica act to template the micropores and mesopores, respectively. It was used as a cathode material for Li-ion battery. Its adsorption behavior and magnetic property was also surveyed. Following this we described the preparation and characterization of mesoporous CuO and reduced Cu[subscript(x)]O, and demonstrated their application in NO adsorption and delivery. Finally a series of crystalline mesoporous metal oxides were prepared and evaluated as catalysts for the CO oxidation.

In the early 1970s, research carried out on rechargeable lithium batteries at the Exxon Laboratories in the US established that lithium ions can be intercalated electrochemically into certain layered transition-metal sulphides, the most promising being titanium disulphide. Stemming from this discovery for titanium disulphide, there has been increased interest on lithium-ion intercalation compounds for application in rechargeable batteries. The first rechargeable lithium cell was commercialized in late 1980s by Moli Energy Corporation in Canada. The cell comprised a spirally wound lithium foil as the anode, a separator and MoS2 as the cathode. The cell had a nominal voltage of 1.8 V and an attractive value of specific energy, which was 2 to 3 times greater than either lead-acid or nickel-cadmium cells. However, the battery was withdrawn from the market after safety problems were experienced. This paved way for the discovery of lithium-ion battery. The origin of lithium-ion battery lies in the discovery that Li+-ions can be reversibly intercalated within or deintercalated from the van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. Thus, lithium metal is replaced by carbon as the anode material for rechargeable lithium-ion batteries, and the problems associated with metallic lithium mitigated. Complimentary investigations on intercalation compounds based on transition metals resulted in establishing LiCoO2 and LiNiO2 as promising cathode materials. By employing aforesaid intercalation materials, namely carbon and LiCoO2 respectively, as negative and positive electrodes in a non-aqueous lithium-salt electrolyte, a Li-ion cell with a voltage value of about 3.5 V resulted. These findings led to a novel rechargeable battery technology. Lithium-ion batteries were first introduced commercially in 1991 by the Sony Corporation in Japan. Other Japanese manufacturers soon entered the market, followed closely by American and European companies. The subsequent growth in sales of the batteries was truly phenomenal. Beginning from 1991, the lithium-ion battery market has grown from an R&D interest to sales of over 400 million units in 1999. The global market value for lithium-ion batteries at original equipment manufacturer level was estimated to be $1.86 billion in 2000. By 2006, the market is expected to grow to over 1.2 billion units with value of over $4 billion, while the average unit price is expected to fall. Initially, realizable specific energy of commercial Li-ion battery was only about 120 Wh kg-1. However, with continuing improvements in various cell components, present day Li-ion batteries can provide a specific energy density of about 200 Wh kg-1. With the ‘holy grail’ far to be realized, the current R&D efforts are focussed on furthering the specific energy of lithium-ion batteries in conjunction with safety, environmental compatibility, and cost effectiveness. In the Li-ion cell, all of its electrochemical constituents, namely anode, cathode and electrolyte are central to its performance. This thesis describes some novel studies on cathode and anode materials for lithium-ion Batteries.

En raison de leurs performances en termes de densités énergétiques et de puissance, les batteries Li-ion sont les systèmes de stockage électrique privilégiés pour les nouvelles générations de véhicules électriques. Leur modélisation est indispensable pour fournir une évaluation de leurs performances tout au long de leur durée de vie tout en limitant le nombre d'essais expérimentaux, et ceci dans le but de concevoir des configurations et des gestions optimales des packs batteries pour une application envisagée. Le but de ce travail consiste à proposer un modèle physique capable de prédire le comportement et le vieillissement de la batterie sous différentes conditions. Un modèle simplifié électrochimique et thermique capable de prédire le comportement physicochimique et le vieillissement de batteries Li-ion a été étudié. Une analyse de sensibilité a été menée sur l'ensemble des paramètres du modèle dans différentes conditions afin de mettre en évidence leurs influences sur les sorties du modèle. Sur cette base, une méthode d'identification a été proposée pour préserver une indépendance des résultats de l'identification paramétrique par rapport à la sensibilité des paramètres. Cette méthode a permis d'améliorer les prédictions de vieillissement avec des estimations très proches des résultats expérimentaux. Au-delà des gains en compréhension et prédiction, ce modèle physique ouvre de nouvelles possibilités pour établir des protocoles de vieillissement accélérés. / Due to their high power and energy densities, Li-ion batteries are the leading systems for the new generations of electric vehicles, for which an optimum cell design, management and configuration is essential. Modeling provides tools to perform complex analysis of the performance of Li-ion batteries and reduces the amount of time spent on experimental testing. The aim of our research is to propose a physics-based model that can predict battery behavior and aging under various conditions during the entire lifespan. A simplified electrochemical and thermal model that can predict both physicochemical and aging behaviors of Li-ion batteries has been studied. A sensitivity analysis of all its physical parameters has been performed in order to find out their influence on the model outputs based on simulations under various conditions. The results gave hints on whether a parameter needs particular attention when measured or identified and on the conditions under which it is the most sensitive. A specific simulation profile has been designed for parameters involved in aging equations in order to determine their sensitivity. Finally, a step-wise method has been followed to limit the influence of parameter values when identifying sorne of them. This sensitivity analysis and the subsequent step-wise identification method show very good results, such as a better fitting of the experimental data with simulated cell voltage. Beyond advanced comprehension and prediction, this physical model opens new possibilities to define accelerated aging tests.

The demands for advanced power sources with high energy efficiency, minimum environmental impact, and low cost have been the impetus for the development of a new generation of batteries and fuel cells. One of the key challenges in this effort is to develop and fabricate effective electrodes with desirable composition, microstructure and performance. This work focused on the design, fabrication, and characterization of nanostructured electrodes in an effort to minimize electrode polarization losses. Solid-state diffusion often limits the utilization and rate capability of electrode materials in a lithium-ion battery, especially at high charge/discharge rates. When the fluxes of Li+ insertion or extraction exceed the diffusion-limited rate of Li+ transport within the bulk phase of an electrode, concentration polarization occurs. Further, large volume changes associated with Li+ insertion or extraction could induce stresses in bulk electrodes, potentially leading to mechanical failure. Interconnected porous materials with high surface-to-volume ratio were designed to suppress the stress and promote mass transport. In this work, electrodes with these unique architectures for lithium ion batteries have been fabricated to improve the cycleability, rate capability and capacity retention. Cathodic interfacial polarization represents the predominant voltage loss in a low-temperature SOFC. For the first time, regular, homogeneous and bimodal porous MIEC electrodes were successfully fabricated using breath figure templating, which is self-assembly of the water droplets in polymer solution. The homogeneous macropores promoted rapid mass transport by decreasing the tortuosity. And mesoporous microstructure provided more surface areas for gas adsorption and more TPBs for the electrochemical reactions. Moreover, composite electrodes were developed with a modified sol-gel process for honeycomb SOFCs. The sol gel derived cathodes with fine grain size and large specific surface area, showed much lower interfacial polarization resistances than those prepared by other existing processing methods. Nanopetals of cerium hydroxycarbonate have been synthesized via a controlled hydrothermal process in a mixed water-ethanol medium. The formation of the cerium compound depends strongly on the composition of the precursors, and is attributed to the favored ethanol oxidation by Ce(IV) ions over Ce(IV) hydrolysis process. Raman studies showed that microflower CeO2 preferentially stabilizes O2 as a peroxide species on its surface for CO oxidation.

Chemo-mechanics studies the material behavior and phenomena at the interface of mechanics and chemistry. Material failures due to coupled chemo-mechanical effects are serious roadblocks in the development of renewable energy technologies. Among the sources of renewable energies for the mass market, hydrogen and lithium-ion battery are promising candidates due to their high efficiency and easiness of conversion into other types of energy. However, hydrogen will degrade material mechanical properties and lithium insertion can cause electrode failures in battery owing to their high mobilities and strong chemo-mechanical coupling effects. These problems seriously prevent the large-scale applications of these renewable energy sources. In this thesis, the atomistic and continuum modeling are performed to study the chemical-mechanical failures. The objective is to understand the hydrogen embrittlement of grain boundary engineered metals and the lithium insertion-induced fracture in alloy electrodes for lithium-ion batteries. Hydrogen in metallic containment systems such as high-pressure vessels and pipelines causes the degradation of their mechanical properties that can result in sudden catastrophic fracture. A wide range of hydrogen embrittlement phenomena was attributed to the loss of cohesion of interfaces (between grains, inclusion and matrix, or phases) due to interstitially dissolved hydrogen. Our modeling and simulation of hydrogen embrittlement will address the question of why susceptibility to hydrogen embrittlement in metallic materials can be markedly reduced by grain boundary engineering. Implications of our results for efficient hydrogen storage and transport at high pressures are discussed. Silicon is one of the most promising anode materials for Li-ion batteries (LIB) because of the highest known theoretical charge capacity. However, Si anodes often suffer from pulverization and capacity fading. This is caused by the large volume changes of Si (~300%) upon Li insertion/extraction close to the theoretical charging/discharging limit. In particular, large incompatible deformation between areas of different Li contents tends to initiate fracture, leading to electro-chemical-mechanical failures of Si electrodes. In order to understand the chemo-mechanical mechanisms, we begin with the study of basic fracture modes in pure silicon, and then study the diffusion induced deformation and fracture in lithiated Si. Results have implications for increasing battery capacity and reliability. To improve mechanical stability of LIB anode, failure mechanisms of silicon and coated tin-oxide nanowires have been studied at continuum level. It's shown that anisotropic diffusivity and anisotropic deformation play vital roles in lithiation process. Our predictions of fracture initiation and evolution are verified by in situ experiment observations. Due to the mechanical confinement of the coating layers, our study demonstrates that it is possible to simultaneously control the electrochemical reaction rate and the mechanical strain of the electrode materials through carbon or aluminum coating, which opens new avenues of designing better lithium ion batteries. This thesis addresses the nano-chemo-mechanical failure problems in two green energy-carrier systems toward improving the performance of Li-ion battery anode and hydrogen storage system. It provides an atomistic and continuum modeling framework for the study of chemo-mechanics of advanced materials such as nano-structured metals and alloys. The results help understand the chemical effects of impurities on the mechanical properties of host materials with different metallic and covalent bonding characteristics.

Indiana University-Purdue University Indianapolis (IUPUI) / Rechargeable lithium ion batteries are widely used in portable consumer electronics such as cellphones, laptops, etc. These batteries are capable to provide high energy density with no memory effect and they have small self-discharge when they are not in use, which increases their potential for future electric vehicles. Investigators are attempting to improve the performance of these cells by focusing on the energy density, cost, safety, and durability. The energy density improves with high operation voltage and high capacity. Before any further development of high voltage materials, safe electrolytes with high ionic conductivity, wide electrochemical window, and high stability with both electrodes need to be developed. In this thesis a new strategy was investigated to develop electrolytes that can contribute to the further development of battery technology. The first study is focused on preparing a hybrid electrolyte, the combination of inorganic solid and organic liquid, for lithium based rechargeable batteries to illustrate the effect of electrode/electrolyte interfacing on electrochemical performance. This system behaves as a self-safety device at higher temperatures and provides better performance in comparison with the solid electrolyte cell, and it is also competitive with the pure liquid electrolyte cell. Then a multilayer electrolyte cell (MEC) was designed and developed as a new tool for investigating electrode/electrolyte interfacial reactions in a battery system. The MEC consists of two liquid electrolytes (L.E.) separated by a solid electrolyte (S.E.) which prevents electrolyte crossover while selectively transporting Li+ ions. The MEC successfully reproduced the performance of LiFePO4 comparable with that obtained from coin cells. In addition, the origin of capacity fading in LiNi0.5Mn1.5O4full-cell (with graphite negative electrode) was studied using the MEC. The performance of LiNi0.5Mn1.5O4 MEC full-cell was superior to that of coin full-cell by eliminating the Mn dissolution problem on graphite negative electrode as evidenced by transmission electron microscopy (TEM) analysis. The MEC can be a strong tool for identifying the electrochemical performances of future high voltage positive electrode materials and their electrode/electrolyte interfacial reactions. Finally, by employing the multilayer electrolyte concept, a new application will be introduced to recycle the lithium. This study demonstrates the feasibility of using water and the contents of waste Li-ion batteries for the electrodes in a Li-liquid battery system. Li metal was collected electrochemically from a waste Li-ion battery containing Li-ion source materials from the battery’s anode, cathode, and electrolyte, thereby recycling the Li contained in the waste battery at the room temperature.

Indiana University-Purdue University Indianapolis (IUPUI) / Due to the drastic increase in the cost of fossil fuels and other environmental issues, the demand for energy and its storage has risen globally. Rather than being dependent on intermittent energy sources like wind and solar energy, focus has been on alternative energy sources. To eliminate the need for fossil fuels, advances are being made to provide energy for hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV) and pure electric vehicles (EV) thus providing scope for much greener environment. Hence, focus has been on development in lithium ion batteries to provide with materials that have high energy density and voltage. Ortho olivine lithium transitional metals are known to be abundant and inexpensive; these compounds are less noxious than other cathode materials. Advancement in research is being done in finding iron and manganese compounds as cathode materials for advanced technologies. However, Lithium manganese phosphates are known to suffer with poor electrochemical performances due the manganese dissolution in the organic liquid electrolyte due to Jahn-Teller Lattice distortion. This problem was tried to endorse in this thesis. In the second chapter by synthesizing nano sized cathode particles with good electronic conductivity, good performance was achieved. In the third chapter additive olivine cathode was synthesized my modified sol gel process. A wt. % of TMSP was added as an additive in the organic liquid electrolyte. By comparing the properties between the two kinds of electrolytes it was observed that by the addition of the additive in the organic electrolyte good electrochemical properties could be achieved hindering the Mn dissolution in the electrolyte. In the final chapter, a composite solid electrolyte was fabricated by using NASICON-type glass ceramic of Lithium aluminum titanium phosphate (LATP) with organic binder of Polyethylene oxide. The flexible solid electrolyte exhibited good ionic conductivity. An all solid state cell was fabricated using the composite solid electrolyte using LiMn2O4 as the symmetric electrodes. At different pressures, the performance of the solid state cell was studied.

Indiana University-Purdue University Indianapolis (IUPUI) / A gradient free function optimization technique, namely particle swarm optimization (PSO) algorithm, is utilized in parameter identification of the electrochemical model of a Lithium-Ion battery having a LiCoO2 chemistry. Battery electrochemical model parameters are subject to change under severe or abusive operating conditions resulting in, for example, Navy over-discharged battery, 24-hr over-discharged battery, and over-charged battery. It is important for a battery management system to have these parameters changes fully captured in a bank of battery models that can be used to monitor battery conditions in real time. In this work, PSO methodology has been used to identify four electrochemical model parameters that exhibit significant variations under severe operating conditions. The identified battery models were validated by comparing the model output voltage with the experimental output voltage for the stated operating conditions. These identified conditions of the battery were then used to monitor condition of the battery that can aid the battery management system (BMS) in improving overall performance. An adaptive estimation technique, namely multiple model adaptive estimation (MMAE) method, was implemented for this purpose. In this estimation algorithm, all the identified models were simulated for a battery current input profile extracted from the hybrid pulse power characterization (HPPC) cycle simulation of a hybrid electric vehicle (HEV). A partial differential algebraic equation (PDAE) observer was utilized to obtain the estimated voltage, which was used to generate the residuals. Analysis of these residuals through MMAE provided the probability of matching the current battery operating condition to that of one of the identified models. Simulation results show that the proposed model based method offered an accurate and effective fault diagnosis of the battery conditions. This type of fault diagnosis, which is based on the models capturing true physics of the battery electrochemistry, can lead to a more accurate and robust battery fault diagnosis and help BMS take appropriate steps to prevent battery operation in any of the stated severe or abusive conditions.