"A ¡°mixed cathodes¡± LIB recycling process was first proposed and developed in the CR3 center at Worcester Polytechnic Institute. This process can efficiently and economically recover all the valuable metal elements in LIB waste. In the end of the recovery process, lithium, nickel, manganese, and cobalt ions will be recovered in the leaching solution. The objective of this work is to utilize the leaching solution to synthesis NixMnyCoz(OH)2 precursors and their corresponding LiNixMnyCozO2 cathode materials. The synthesized cathode materials can be used to build new LIBs, allowing the overall process to be a ¡°closed loop¡±. "

The main aim of this thesis is to reveal the chemical structures of the solid-liquid interphase in lithium ion batteries by NMR spectroscopy in order to understand the working mechanism of electrolyte additives for achieving stable cycling performance. In the first part, a combination of solution and solid-state NMR techniques, including dynamic nuclear polarization (DNP) are employed to monitor the formation of the solid electrolyte interphase (SEI) on next-generation, high-capacity Si anodes in conventional carbonate electrolytes with and without fluoroethylene carbonate (FEC) additives. A model system of silicon nanowire (SiNW) electrode is used to avoid interference from the polymeric binder. To facilitate characterization via one- and two-dimensional NMR, ^13C-enriched FEC was synthesized and used, ultimately allowing a detailed structural assignment of the organic SEI. FEC is found to first defluorinated to form soluble vinylene carbonate (VC) and vinoxyl species, which react to form both soluble and insoluble branched ethylene-oxide-based polymers. In the second part, the same methodology is applied to study the decomposition products of pure FEC or VC electrolytes containing 1 M LiPF_6. The pure FEC/VC system simplifies the electrolyte solvent formulation and avoids the interaction between different solvent molecules. Polymeric SEIs formed in pure FEC or VC electrolytes consist mainly of cross-linked PEO and aliphatic chain functionalities along with additional carbonate and carboxylate species. The presence of cross-linked PEO-type polymers in FEC and VC correlates with good capacity retention and high Coulombic efficiencies of the SiNWs anode. Using ^29Si DNP NMR, the interfacial region between SEI and the Si surface was probed for the first time with NMR spectroscopy. Organosiloxanes form upon cycling, confirming that some of the organic SEI is covalently bonded to the Si surface. It is suggested that both the polymeric structure of the SEI and the nature of its adhesion to the redox-active materials are important for electrochemical performance. Finally, the soluble decomposition products of EC formed during electrochemical cycling have been thoroughly analyzed by solution NMR and mass spectrometry, in order to explain the capacity-fading of Si anodes in a conventional EC-based electrolyte and address questions that arose when studying the additive-containing electrolytes. The detailed structures for the EC-degradation products are determined: a linear oligomer consist of ethylene oxide and carbonate units is observed as the major degradation product of EC.

Silicon has the highest theoretical capacity of any known anode material, and silicon coated carbon nanotubes (Si-CNTs) have shown promise of dramatically increasing battery capacity. However, capacity fading with cycling and low rate capability prevent widespread use. Here, three studies on differing aspects of these batteries are presented. Here, three studies on differing aspects of these batteries are presented. The first examines the rate capability of these batteries. It compares the cycling of electrodes hundreds of microns thick with and without ten micron access holes to facilitate diffusion. The holes do not improve rate capability, but thinner coatings of silicon do improve rate capability, indicating that the limiting mechanism is the diffusion through the nanoscale bulk silicon. The second attempts to enable stable cycling of anodes heavily loaded with silicon, using a novel monolithic scaffolding formed by coating vertically aligned carbon nanotubes (VACNTs) with nanocrystalline carbon. The structure was only able to stabilize the cycling at loadings of carbon greater than 60% of the electrode by volume. These electrodes have volume capacities of ~1000 mAhr/ml and retained over 725 mAhr/ml by cycle 100. The third studies the use of an encapsulation method to stabilize the solid electrolyte interphase (SEI) and exclude the electrolyte. The method was only able to stabilize cycling at loadings below 5% silicon, but exhibits specific capacities as high as 3000 mAhr/g of silicon after 20 cycles.

archives@tulane.edu / This dissertation utilizes molecular theory and simulations to study thermodynamics of ions in electrolyte solutions of practical interest. The first half of this work focuses on two important electrochemical energy storage systems: Lithium ion batteries and supercapacitors based on carbon nanotube (CNT) forests. In lithium ion batteries, the characteristics of Li+ transport are studied in the solid electrolyte interphase of batteries. This study has potential applications in the design and theoretical testing of novel fast-charging batteries. The work on CNT supercapacitor focuses on the dependence of capacitance on pore spacing and electrode potentials. In the second half, the hydration of halides (fluoride and chloride) are studied using Quasi-chemical theory (QCT). Here, refinements in the implementation of QCT are pursued, leading to free energies that are in excellent agreement with experiments. This advancement should be helpful to address issues such as Hofmeister effects and selectivity in ion channels. / 1 / Ajay Muralidharan

<p>The lucrative characteristics of high energy and power density from lithium-ion batteries have also become drawbacks when they are not handled appropriately. The reactive and flammable materials present within the cell raise safety concerns which need to be addressed. Aging of the cell components occurs in a natural way due to continuous cycling. Constant intercalation/deintercalation of Li-ions into the active materials induces stresses that in the long-term cycling mechanically modify the electrodes in an irreversible way. Also, electrode/electrolyte side reactions diminish the Li-ion inventory reducing the cell capacity and lifetime. Along with cell aging, intentional/unintentional abuse tests can occur at the hands of the final user. Improper handling and operation may lead the Li-ion cell to failure and possibly going into thermal runaway. This condition represents a threat to safety not only for cell integrity but also for user safety. Failure event can occur not only in brand new cells but also in aged cells. Current degradation studies focus either on the long-term aging degradation mechanisms or on fresh new cells’ abuse test. And few of them focused on the combination of both of them. </p>In this work, the degradation of Li-ion cells is investigated at different levels. First, at the electrode level, the effect of electrode processing and the intercalation properties of an anode and cathode materials is investigated. Then, at the cell level, abuse conditions such as external short, overcharge and overdischarge are studied in fresh and aged cells with different levels of degradation. Last but not least, the cells are assembled in a module configuration to investigate how a minor difference from one cell to another can affect the long-term performance. The aim is accomplished via a controlled lab test approach in order to get insights about the electrochemical, thermal and morphological changes that take place when the cell degrades.<br>

>Magister Scientiae - MSc / Lithium iron manganese phosphate (LiFe0.5Mn0.5PO4), is a promising, low cost and high energy density (700 Wh/kg) cathode material with high theoretical capacity and high operating voltage of 4.1 V vs. Li/Li+, which falls within the electrochemical stability window of conventional electrolyte solutions. However, a key problem prohibiting it from large scale commercialization is its severe capacity fading during cycling. The improvement of its electrochemical cycling stability is greatly attributed to the suppression of Jahn-Teller distortion at the surface of the LiFe0.5Mn0.5PO4 particles. Nanostructured materials offered advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The LiFe0.5Mn0.5PO4 nanoparticles were synthesized via a simple-facile microwave method followed by coating with multi-walled carbon nanotubes (MWCNTs) nanoparticles to enhance electrical and thermal conductivity. The pristine LiFe0.5Mn0.5PO4 and LiFe0.5Mn0.5PO4-MWCNTs composite were examined using a combination of spectroscopic and microscopic techniques along with electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiFe0.5Mn0.5PO4-MWCNTs composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiFe0.5Mn0.5PO4 due to the presence of the conductive additives in the LiFe0.5Mn0.5PO4-MWCNTs composite. For the composite cathode, D = 2.0 x 10-9 cm2/s while for pristine LiFe0.5Mn0.5PO4 D = 4.81 x 10-10 cm2/s. The charge capacity and the discharge capacity for LiFe0.5Mn0.5PO4-MWCNTs composite were 259.9 mAh/g and 177.6 mAh/g, respectively, at 0.01 V/s. The corresponding values for pristine LiFe0.5Mn0.5PO4 were 115 mAh/g and 44.75 mAh/g, respectively. This was corroborated by EIS measurements. LiFe0.5Mn0.5PO4-MWCNTs composite showed to have better conductivity which corresponded to faster electron transfer and therefore better electrochemical performance than pristine LiFe0.5Mn0.5PO4. The composite cathode material (LiFe0.5Mn0.5PO4-MWCNTs) with improved electronic conductivity holds great promise for enhancing electrochemical performances and the suppression of the reductive decomposition of the electrolyte solution on the LiFe0.5Mn0.5PO4 surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiFe0.5Mn0.5PO4 nano-powder cathode material. / 2023-12-01

Batteries have found wide use in many household and industrial applications and since the 1990s, they have continued to rapidly shape the economy and social landscape of humans. Lithium ion batteries, a type of rechargeable batteries, have experienced a leap-frog development at technology and market share due to their prominent performance and environmental advantages and therefore, different forecasts have been made on the future trend for the lithium ion batteries in-terms of their use. The steady growth of energy demand for consumer electronics (CE) and electric vehicles (EV) have resulted in the increase of battery consumption and the electric vehicle (EV) market is the most promising market as it will consume a large amount of the lithium ion batteries and research in this area has reached advanced stages. This will consequently be resulting in an increase of metal-containing hazardous waste. Thus, to help prevent environmental and raw materials consumption, the recycling and recovery of the major valuable components of the spent lithium ion batteries appears to be beneficial. In this thesis, it was attempted to recover lithium from a synthetic slag produced using pyrometallurgy processing and later treated using hydrometallurgy. The entire work was done in the laboratory to mimic a base metal smelting slag. The samples used were smelted in a Tamman furnace under inert atmosphere until 1250oC was reached and then maintained at this temperature for two hours. The furnace was then switched off to cool for four hours and the temperature gradient during cooling was from 1250oC to 50oC. Lime was added as one of the sample materials to change the properties of the slag and eventually ease the possibility of selectively leaching lithium from the slag. It was observed after smelting that the slag samples had a colour ranging from dark grey to whitish grey among the samples.The X - ray diffractions done on the slag samples revealed that the main phases identified included fayalite (Fe2SiO4), magnetite (Fe3O4), ferrobustamine (CaFeO6Si2), Kilchoanite (Ca3Si2O7), iron oxide (Fe0.974O) and quartz (SiO2). The addition of lime created new compound in the slag with the calcium replacing the iron. The new phases formed included hedenbergite (Ca0.5Fe1.5Si2O6), ferrobustamine (CaFeO6Si2), Kilchoanite (Ca3Si2O7) while the addition of lithium carbonate created lithium iron (II) silicate (FeLi2O4Si) and dilithium iron silicate (FeLi2O4Si) phases.The Scanning Electron Microscopy (SEM) micrographs of the slag consisted mainly of Fe, Si and O while the Ca was minor. Elemental compositions obtained after analysis was used to identify the different phases in all the slag samples. The main phases identified were the same as those identified by the XRD analysis above except no phase with lithium was identified. No lithium was detected by SEM due to the design of the equipment as it uses beryllium planchets which prevent the detection of lithium.Leaching experiments were done on three slag samples (4, 5 and 6) that had lithium carbonate additions. Leaching was done for four hours using water, 1 molar HCl and 1 molar H2SO4 as leaching reagents at room temperature. Mixing was done using a magnetic stirrer. The recoveries obtained after leaching with water gave a lithium recovery of 0.4%. Leaching with HCl gave a recovery of 8.3% while a recovery of 9.4% was obtained after leaching with H2SO4.It can be concluded that the percentage of lithium recovered in this study was very low and therefore it would not be economically feasible. It can also be said that the recovery of lithium from the slag system studied in this work is very difficult because of the low recoveries obtained. It is recommended that test works be done on spent lithium ion batteries so as to get a better understanding of the possibilities of lithium recovery as spent lithium ion batteries contain other compounds unlike the ones investigated in this study.

<p>The current work focuses on the synthesis and characterization of nano-devices with potential application in alkaline electrolysis and secondary polymer lithium ion batteries.</p>

Electric and hybrid electric vehicles are gaining momentum as a sustainable alternative to conventional combustion based transportation. The operating temperature of the vehicle will vary significantly over the vehicle lifetime and this variance in operating temperature will strongly impact the performance, driving range, and durability of batteries used in the vehicles. In the first part of this thesis, an experimental facility is developed to accurately quantify the effects of battery operating temperature on discharge characteristics through precise control of the battery operating temperatures, utilizing a water-ethylene glycol solution in a constant temperature thermal bath. A prismatic 20Ah LiFEPO4 battery from A123 is tested using the developed method, and temperature measurements on the battery throughout discharge show a maximum variation of 0.3°C temporally and 0.4°C spatially at a 3C discharge rate, in contrast to 13.1°C temperature change temporally and 4.3°C spatially when using the conventional air convection temperature control method under the same test conditions. A comparison of battery discharge curves using the two methods show that the reduction in spatial and temporal temperature change in the battery has a large effect on the battery discharge characteristics. The developed method of battery temperature control yields more accurate battery discharge characterization due to both the elimination of state-of-charge drift caused by spatial variations in battery temperature, and inaccurate discharge characteristics due to battery heat up at various discharge and ambient conditions. Battery discharge characterization performed using the developed method of temperature control exhibits a reduction in battery capacity of 95% when the operating temperature is decreased from 20°C to -10°C at 3C discharge rate. A reduction of 35% in battery capacity is observed when for the same temperature decrease at a 0.2C discharge rate. The observed effect of operating temperature on the capacity of the tested battery highlights the importance of an effective thermal management system, the design of which requires accurate knowledge of the heat generation characteristics of the battery under various discharge rates and operating temperatures. In the second part of this thesis, a calorimeter capable of measuring the heat generation rates of a prismatic battery is developed and verified by using a controllable electric heater. The heat generation rate of a prismatic A123 LiFePO4 battery is measured for discharge rates ranging from 0.25C to 3C and operating temperature ranging from -10°C to 40°C. Results show that the heat generation rates of Lithium ion batteries are greatly affected by both battery operating temperature and discharge rate. At low rates of discharge the heat generation is not significant, even becoming endothermic at the battery operating temperatures of 30°C and 40°C. Heat of mixing is observed to be a non-negligible component of total heat generation at discharge rates as low as 0.25C for all tested battery operating temperatures. A double plateau in battery discharge curve is observed for operating temperatures of 30°C and 40°C. The developed experimental facility can be used for the measurement of heat generation for any prismatic battery, regardless of chemistries. The characterization of heat generated by the battery under various discharge rates and operating temperatures can be used to verify the accuracy of battery heat generation models currently used, and for the design of an effective thermal management system for electric and hybrid electric vehicles in the automotive industry.

This study highlights the importance of the anion in the electrochemical uptake of lithium by metal phosphides. It is shown through a variety of <em>in-situ</em> and <em>ex-situ</em> analytical techniques that the redox active centers in three different systems (MnP<i>₄</i>, FeP<i>₂</i>, and CoP<i>₃</i>) are not necessarily cationic but can rest almost entirely upon the anionic network, thanks to the high degree of covalency of the metal-phosphorus bond and strong P-character of the uppermost filled electronic bands in the phosphides. The electrochemical mechanism responsible for reversible Li uptake depends on the transition metal, whether a lithiated ternary phase exists in the phase diagram with the same M:P stoichiometry as the binary phase, and on the structure of the starting phase. When both binary and lithiated ternary phases of the transition metal exist, as in the case of MnP<i>₄</i> and Li<i>₇</i>MnP<i>₄</i>, a semi-topotactic phase transformation between binary and ternary phases occurs upon lithium uptake and removal. When only the binary phase exists two different behaviours are observed. In the FeP<i>₂</i> system, lithium uptake leads to the formation of an amorphous material in which short-range order persists; removal of lithium reforms some the long-range order bonds. In the case of CoP<i>₃</i>, lithium uptake results in phase decomposition to metallic cobalt plus lithium triphosphide, which becomes the active material for the subsequent cycles.