Lithium alloys with metallic or semi-metallic elements are attractive candidate materials for the next-generation rechargeable Li-ion battery anodes, thanks to their large specific and volumetric capacities. The key challenge, however, has been the large volume changes, and the associated stress buildup and failure during cycling. The chemo-mechanics of alloy-based electrode materials entail interactions among diffusion, chemical reactions, plastic flow, and material property evolutions. In this study, a continuum theory of two-way coupling between diffusion and deformation is formulated and numerically implemented. Analyses based on this framework reveal three major conclusions. First, the stress-to-diffusion coupling in Li/Si is much stronger than what has been known in other electrode materials. Practically, since the beneficial effect of stress-enhanced diffusion is more pronounced at intermediate or higher concentrations, lower charging rates should be used during the initial stages of charging. Second, when plastic deformation and lithiation-induced softening take place, the effect of stress-enhanced diffusion is neutralized. Because the mechanical driving forces tend to retard diffusion when constraints are strong, even in terms of operational charging rate alone, Li/Si nano-particles are superior to Li/Si thin films or bulk materials. Third, the diffusion of the host atoms can lead to significant stress relaxation even when the stress levels are below the yield threshold of the material, a beneficial effect that can be leveraged to reduce stresses because the host diffusivity in Li/Si can be non-negligible at higher Li concentrations. A theory of coupled chemo-mechanical fracture driving forces is formulated in order to capture the effect of deformation-diffusion coupling and lithiation-induced softening on fracture. It is shown that under tensile loading, Li accumulates in front of crack tips, leading to an anti-shielding effect on the energy release rate. For a pre-cracked Li/Si thin-film electrode, it is found that the driving force for fracture is significantly lower when the electrode is operated at higher Li concentrations -- a result of more effective stress relaxation via global yielding. The results indicate that operation at higher concentrations is an effective means to minimize failure of thin-film Li/Si alloy electrodes.

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.

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.

Subsequent to the studies on precursor lead-acid systems by Daniel, Grove and Sindesten, practical lead-acid batteries began with the research and inventions of Raymond Gaston Planté in France as early as in 1859, and, even to-day, lead-acid battery remains the most successful battery system ever developed, and no other battery is yet able to compete with lead-acid batteries on cost grounds, albeit batteries based on other chemistries are rapidly catching up. In the past, although lead-acid battery designs have been optimized in several different directions, there are still certain new challenges facing the lead-acid battery designers as additional failure modes become evident in various use modes. There are three types of lead-acid batteries in common use: (a) batteries with flooded or excess electrolyte, (b) low-maintenance lead-acid batteries with a large excess of electrolyte, and (c) batteries with immobilized electrolyte and a pressure-sensitive valve usually referred to as absorptive glass-microfibre (AGM) valve-regulated lead-acid (VRLA) batteries. The flooded-electrolyte lead-acid battery requires checking of specific gravity of electrolyte, periodic addition of water to maintain electrolyte level above the plates and recharge soon after discharge to prevent hard sulfation that causes loss of capacity. The emission of acid fumes corrodes metallic parts in the vicinity of the battery, and the seepage of acid on the top cover of the batteries leads to leakage current resulting in increased self-discharge and ground-shunt hazards. To overcome these problems, AGMVRLA batteries based on oxygen-recombination cycle have emerged. These batteries offer the freedom of battery placement, cyclability without the addition of water or checking the specific gravity, increased safety, and superior performance in some instances. Both flooded-electrolyte and AGM-VRLA batteries can suffer from acid stratification. But, AGM-VRLA batteries are especially susceptible to failures owing to the heat generated by oxygen recombination within the cells as well as due to cell-to-cell variations in electrolyte volumes. Indeed, partial heating of AGM-VRLA batteries could cause dry-out with grid corrosion and even lead to thermal runaway. Consequently, mitigating temperature variations in AGM-VRLA batteries becomes seminal to their commercial success. A dissipation of local heat within the AGM-VRLA batteries can be achieved by adequately filling the void volume in the battery with a thermally conducting gel, such as a gel formed from colloidal silica and sulfuric-acid electrolyte. Although, conventional lead-acid batteries are considered rather a matured technology, significant research and development efforts are currently under way to enhance their performance. Indeed, many improvements have been made in the lead-acid battery since its invention, and although the essential electrochemistry remains unchanged, the modern lead-acid batteries have little semblance to those produced 50 years ago. Over the years, seminal advances have been made in the lead-alloys used, in the materials and design of separators, in battery packaging and in their construction methods, which have led to lead-acid batteries with improved performance, lighter weight and lower cost. This thesis is an attempt to develop lightweight hybrid-VRLA batteries.

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) / Lithium-ion battery is one kind of rechargeable battery, and also renewable, sustainable and portable. With the merits of high density, slow loss of charge when spare and no memory effect, lithium-ion battery is widely used in portable electronics and hybrid vehicles. Apart from its advantages, safety is a major concern for Lithium-ion batteries due to devastating incidents with laptop and cell phone batteries. Overcharge and over-discharge are two of the most common electrical abuses a lithium-ion battery suffers. In this thesis, a fuzzy-rule-based system is proposed to detect the over-charge and over-discharge failure in early time. The preliminary results for the failure signatures of overcharged and over-discharged lithium-ion are listed based on the experimental results under both room temperature and high temperature. A fuzzy-rule-based model utilizing these failure signatures is developed and validated. For over-charge case, the abnormal increase of the surface temperature and decrease of the voltage are captured. While for over discharge case, unusual temperature increase during overcharge phases and abnormal current decrease during overcharge phases are obtained. The inference engine for fuzzy-rule-based system is designed based on these failure signatures. An early warning signal will be given by this algorithm before the failure occurs. This failure detection and early warning system is verified to be effective through experimental validation. In the validation test, the proposed methods are successfully implemented in a real-time system for failure detection and early warning. The result of validation is compatible with the design expectation. Finally an accurate failure detection and early warning system is built and tested successfully.