Indiana University-Purdue University Indianapolis (IUPUI) / With the exponential rise in manufacturing and usage of Li-ion batteries (LIBs) in the last decade, a huge quantity of spent LIBs is getting scrapped every year. Along with the efforts to making more capable and safer batteries over the last three decades, there is an immediate need for recycling these scrapped batteries. Most of these batteries typically use lithium manganese oxide (LMO), lithium cobalt oxide (LCO), lithium iron phosphate (LFP), and lithium nickel manganese cobalt oxide (NMC) cathode chemistries, and developing a technique towards regenerating these cathodes can ensure huge economic and environmental benefits for the present and future. This research focuses on a set of direct regeneration techniques with the goal of regenerating used cathode materials to be reused in LIBs. Used Apple iPad2 batteries with LCO chemistry and Nissan LEAF batteries with a combination of LMO-NMC chemistry are selected for this research. The scope of research can be divided into two parts as liberation/separation of cathode material and regeneration of liberated cathode. The liberation/separation process is carried out with the aid of ultrasonication and organic solvents with the objective being keeping the morphology and chemical composition intact for a better quality of the material. The regeneration process uses a hydrothermal technique with variations of parameters. 1:1 and 1:5 molar ratios between cathode material and a lithium lithiation agent are chosen to understand the effects of the molar ratio on cathode regeneration. In addition, the effects of processing solution (water vs. a solvent) are examined by replacing water with TEG. The effects of heat treatment on cathode regeneration are also investigated by observing phase changes of materials at different temperatures.

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

<p>The lithium ion battery is today mainly used in cell phonesand laptops. In the future, this kind of battery might beuseful in hybrid electric vehicles as well.</p><p>In this work, the main focus has been to gain more knowledgeabout the lithium ion battery in the hybrid electric vehicle(HEV) and more precisely to examine what processes of thebattery that are limiting at HEV currents. Both experiments andmathematical modelling have been used. In both cases, highrate, pulsed currents typical for the HEV, have been used.</p><p>Two manuscripts have been written. Both of them concern thebehaviour of the battery at HEV load, but from different pointsof view. The first one concerns the electrochemical behaviourof the battery at different ambient temperatures. Theexperimental results of this paper were used to validate amathematical model of a Li-ion battery. Possiblesimplifications of the model were identified. In this work itwas also concluded that the mass transfer of the electrolyte isthe main limiting process within the battery. The mass transferof the electrolyte was further studied in the second paper,where the concentration of lithium ions was measured indirectlyusing in situ Raman spectroscopy. This study showed that themathematical description of the mass transfer of theelectrolyte is not complete. One main reason of this issuggested to be the poor description of the physical parametersof the electrolyte. These ought to be further studied in orderto get a better fit between concentration gradients predictedby experiments and model respectively.</p>

The demand for high performance Lithium-ion batteries (LIBs) is increasing due to widespread use of portable devices and electric vehicles. Silicon (Si) is one of the most attractive candidate anode materials for the next generation LIBs because of its high theoretical capacity (3,578 mAh/g) and low operation potential (~0.4 V vs Li+/Li). However, the high volume change (>300%) during Lithium ion insertion/extraction leads to poor cycle life. The goal of this work is to improve the electrochemical performance of Si/C composite anode in LIBs. Two strategies have been employed: to explore spatial arrangement in micro-sized Si and to use Si/graphene nanocomposites. A unique branched microsized Si with carbon coating was made and demonstrated promising electrochemical performance with a high active material loading ratio of 2 mg/cm2, large initial discharge capacity of 3,153 mAh/g and good capacity retention of 1,133 mAh/g at the 100th cycle at 1/4C current rate. Exploring the spatial structure of microsized Si with its advantages of low cost, easy dispersion, and immediate compatibility with the prevailing electrode manufacturing technology, may indicate a practical approach for high energy density, large-scale Si anode manufacturing. For Si/Graphene nanocomposites, the impact of particle size, surface treatment and graphene quality were investigated. It was found that the electrochemical performance of Si/Graphene anode was improved by surface treatment and use of graphene with large surface area and high defect density. The 100 nm Si/Graphene nanocomposites presented the initial capacity of 2,737 mAh/g and good cycling performance with a capacity of 1,563 mAh/g after 100 cycles at 1/2C current rate. The findings provided helpful insights for design of different types of graphene nanocomposite anodes.

No description available.

Répondre aux besoins croissants en termes de stockage électrochimique sans épuiser les ressources naturelles exige de promouvoir des technologies de batteries en rupture à la fois efficientes mais aussi à faible impact au plan environnemental. La conception de batteries organiques pourrait s'avérer être une partie de la solution. En effet, la richesse de la chimie organique offre une multitude de possibilités pour développer des matériaux d'électrode innovants à partir d’éléments abondants et peu coûteux. Près de 40 ans après la découverte des polymères conducteurs, des batteries Li-organiques offrent maintenant d’intéressantes performances en cyclage. Pourtant, la synthèse de matériaux organiques lithiés électroactifs à haut-potentiel ainsi que celle de matériaux organiques de type p électroactifs à bas potentiel se sont avérées assez complexes et par conséquent, très peu d'exemples de cellules « tout organique » existent. Au cours de ce travail de recherche, nous avons mis en lumière une approche chimique originale consistant à perturber la structure électronique de l’entité organique électroactive (modulation des effets inductifs) au moyen d’un cation spectateur faiblement électropositif ce qui conduit à une augmentation significative du potentiel redox des matériaux d'électrodes organiques lithiés déjà connus. Cette découverte nous a permis de développer une batterie Li-ion « tout organique » capable d’offrir une tension de sortie d’au moins 2,5 V sur plus de 300 cycles. Ensuite, nous avons cherché à concevoir des matériaux de type p capables de fonctionner à bas potentiel et ainsi élaboré des batteries Anion-ion « tout organique ». Enfin, une étude préliminaire d’une nouvelle famille de composés potentiellement bipolaires au plan redox (intégration de centres redox de type n et de type p) a également été réalisée. / Meeting the ever-growing demand for electrical storage devices, without depleting natural resources, requires both superior and “greener” battery technologies. Developing organic batteries could well provide part of the solution since the richness of organic chemistry affords us a multitude of avenues for uncovering innovative electrode materials based on abundant, low-cost chemical elements. Nearly 40 years after the discovery of conductive polymers, long cycling stability in Li-organic batteries has now been achieved. However, the synthesis of high-voltage lithiated organic cathode materials and the synthesis of low-voltage p type organic anode materials is still rather challenging, so very few examples of all-organic cells currently exist. Herein, we first present an innovative approach consisting in the substitution of spectator cations and leading to a significant increase of the redox potential of lithiated organic electrode materials thanks to an inductive effect. These results enable developing an all-organic Li-ion battery able to deliver an output voltage above 2.5 V for more than 300 cycles. We then design two p type organic electrode materials able of being charged at low potentials for developing all-organic Anion-ion batteries able to deliver an output voltage at least 1.5 V. Finally, we present a preliminary study of a new family of potentially bipolar compounds.

Aluminum based amorphous metallic glass powders were produced and tested as the anode materials for the lithium ion rechargeable batteries. Ground Al₈₀Ni&#x2081₀La&#x2081₀ was found to have a low first cycle capacity of about 100 Ah/Kg. The considerable amount of intermetallic formed in the amorphous glass makes the aluminum inactive towards the lithium. The ball milled Al₈₈Ni₉Y₃ powders contain pure aluminum crystalline particles in the amorphous matrix and have first cycle capacity of about 500 Ah/Kg. Nevertheless, polarization was caused by oxidation introduced by the ball-milling process. The electrochemical performances of these amorphous metallic glasses need to be further investigated. Their full lithium insertion capacities cannot be confirmed until the compositions and particle size inside the metallic glass anodes, the conformation of the electrodes and the mechanical milling processes are optimized. / Singapore-MIT Alliance (SMA)

Lithium ion battery systems are promising solutions to current energy storage needs due to their high operating voltage and capacity. Numerous efforts have been conducted to model these systems in order to aid the design process and avoid expensive and time consuming prototypical experiments. Of the numerous processes occurring in these systems, solid state transport in particular has drawn a large amount of attention from the research community, as it tends to be one of the rate limiting steps in lithium ion battery performance. Recent studies have additionally indicated that purposeful design of battery electrodes using 3D microstructures offers new freedoms in design, better use of available cell area, and increased battery performance. The following study is meant to serve as a first principles investigation into the behaviors of 3D electrode architectures by monitoring concentration and cycle behaviors under realistic operating conditions. This was accomplished using computational tools to model the solid state diffusion behavior in several generated electrode morphologies. Developed computational codes were used to generate targeted structures under prescribed conditions of particle shape, size, and overall morphology. The diffusion processes in these morphologies were simulated under conditions prescribed from literature. Primary results indicate that parameters usually employed to describe electrode geometry, such as volume to surface area ratio, cannot be solely relied upon to predict or characterize performance. Additionally, the interaction between particle shapes implies some design aspects that may be exploited to improve morphology behavior. Of major importance is the degree of particle isolation and overlap in 3D architectures, as these govern gradient development and lithium depletion within the electrode structures. The results of this study indicate that there are optimum levels of these parameters, and so purposeful design must make use of these behaviors.

The Li-ion field of battery research has in the latest decades made substantial progress and is seen to be the most promising battery technology due to the high volume and specific energy densities of Li-ion batteries. However, in order to achieve a battery capable of competing with the energy density of a combustion engine, further research into new electrode materials is required. As the cathode materials are the limiting factor in terms of capacity, this is the main area in need of further research. The introduction of 3-D electrodes brought new hope as the ion transportpath is decreased as well as an increased electrode area leading to an increased capacity. This thesis work has focused on the development of aluminium 3-D current collectors in order to improve the electrode area and shorten the Li-ion transportpath. By using a template assisted electrodeposition technique, nanorods of controlled magnitude and order can be synthesized. Furthermore, the electrodeposition brings excellent possibilities of upscaling for future industrial manufacturing of the batterycells. A polycarbonate template material which showed interesting properties,was used in the electrodeposition of aluminium nanorods. As the template pores were nonhomogeneously ordered a number of nonordered nanorods were expected to arise during the deposition. However, a surplus of nanorods in reference to the template pores was acquired. This behavior was investigated and a hypothesis was formed as to the mechanism of the nanorod formation. In order to achieve acomplete cathode electrode, a coating of an ion host material on the nanorods isneeded. Due to its high capacity and voltage, vanadium oxide was selected. Based on previous work with electrodeposition of V2O5 on platinum, a series of experiments were performed to mimic the deposition on an aluminium sample. Unfortunately, the deposition was unsuccessful as the experimental conditions resulted in aluminium corrosion which in turn made deposition of the cathode material impossible. The pH dependence of the deposition was evaluated and the conclusion was drawn, that electrodeposition of vanadium oxide on aluminium is not possible using this approach.

Transport of ions and molecules in solids is a very important process in many technological applications, for example, in drug delivery, separation processes, and in power sources such as ion diffusion in electrodes or in solid electrolytes. Progress in the understanding of the ionic and molecular transport mechanisms in solids can be used to substantially increase the performance of devices. In this dissertation we use ab initio calculations and molecular dynamics simulations to investigate the mechamisn of transport in solid. We first analyze molecular transport and storage of H2. Different lightweight carbon materials have been of great interest for H2 storage. However, pure carbon materials have low H2 storage capacity at ambient conditions and cannot satisfy current required storage capacities. Modification of carbon materials that enhance the interaction between H2 and absorbents and thus improve the physisorption of H2, is needed for hydrogen storage. In this dissertation, corannulene and alkali metal-doped corannulene are investigated as candidate materials for hydrogen storage. Molecularalso investigated. Using computational chemistry, we predict enhanced H2 adsorption on molecular systems with modification and hydrogen uptake can reach DOE target of 6.5wt% at at 294 bar at 273 K, and 309 bar at 300 K. In the second part of this dissertation, we study the lithium ion transport from a solid electrolyte phase to a solid electrode phase. Improvement of ionic transport in solid electrolytes is a key element in the development of the solid lithium ion batteries. One promising material is dilithium phthalocyanine (Li2Pc), which upon self-assembly may form conducting channels for fast ion transport. Computational chemistry is employed to investigate such phenomena: (1) to analyze the crystalline structure of Li2Pc and formation of conducting channels; (2) to understand the transport of Li ions inside channels driven by an electric field; (3) to study the continuity of the conducting channels through interface. The study shows Li2Pc has higher conductivity than PEO as electrolyte.