Made available in DSpace on 2018-08-01T21:58:48Z (GMT). No. of bitstreams: 1 tese_10827_Dissertação Jenifer Rigo Almeida - FINAL.pdf: 2105933 bytes, checksum: 17fccc5751be81765e75282388ce4b0c (MD5) Previous issue date: 2017-03-27 / Baterias de íon-Lítio (LIBs) exauridas são consideradas resíduos sólidos perigosos devido à presença de metais e compostos orgânicos em sua composição, representando desperdício de recursos naturais não renováveis e de metais valiosos quando descartadas. Este trabalho tem por objetivo fornecer dados quantitativos sobre a composição química do material ativo do cátodo (MAC) de diferentes LIBs exauridas visando monitorar variações com o passar dos anos e auxiliar nos processos de reciclagem do material. Os elementos Al, Co, Cr, Cu, Ga, Li, Mg, Mn, Ni, Ti e Zn foram determinados por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) após lixiviação ácida empregando 2,0 mol.L-1 de ácido cítrico (HCit) e H2O2 (0,25 mol.L-1) como alternativa ambientalmente favorável. As condições otimizadas para adequação do meio às curvas analíticas foram: para Al, Cu: Curva de HCit diluído 10 vezes sem padrão interno (PI); para Co, Li, Mn, Ni: Curva de HCit diluído 500 vezes sem PI; para Ga, Zn: Curva de HCit diluído 10 vezes com Y. O procedimento analítico empregado alcançou limites de detecção de 0,01 mg.L-1 para Al; 0,20 mg.L-1 para Co; 0,006 mg.L-1 para Cr; 0,02 mg.L-1 para Cu; 0,004 mg.L-1 para Ga; 0,02 mg.L-1 para Li; 0,0005 mg.L-1 para Mg; 0,07 mg.L-1 para Mn; 0,70 mg.L-1 para Ni; 0,0005 mg.L-1 para Ti e 0,007 mg.L-1 para Zn. A exatidão do procedimento foi confirmada por testes de adição e recuperação dos analitos obtendo-se valores entre 92-113 %. Os elementos majoritários Co (43-67 % m/m), Li (5,3-6,8 % m/m), Mn (0,8-8,2 % m/m), Ni (0,1-11,7 % m/m) e Al (0,06-3,2 % m/m) e os elementos minoritários Cr (0,0005-0,002 % m/m), Cu (0,01-0,05 % m/m), Mg (0,005-0,02 % m/m), Ti (0,001-0,07 % m/m), Ga (0,0009-0,03 % m/m) e Zn (0,009-0,05 % m/m) demonstraram que a composição do MAC pode variar de acordo com a capacidade e ano de fabricação. As baterias mais antigas foram as que apresentaram maiores teores de Co e Li. As baterias de menor capacidade foram as que continham os maiores teores de Mn e Ni, indicando que o Co foi substituído. O pó do MAC e o resíduo após lixiviação foram caracterizados por difratometria de raios X (DRX) obtendo-se LiCoO2 como composto principal, podendo ser reutilizado.

This thesis is dedicated to developing three different types of ferrocene-containing polymers for organic lithium-ion battery and resistive memory applications. Chapter 1 gives an overview of organic cathode-active materials, polymeric resistive memories and ferrocene-containing polymers. Furthermore, the previously reported applications of ferrocene-containing polymeric systems in electrochemical energy storage and electronical memory devices were also comprehensively summarized. In chapter 2, conjugated ferrocene-containing side-chain metallopolymers PFcFE1, PFcFE2, PFcFE3 and PFcFE4 were designed and synthesized via Sonogashira cross-coupling polycondensation. The charging-discharging processes of triphenyamine-based PFcFE1 and thiophene-modified PFcFE4 have been successfully studied as cathode materials. PFcFE1 composite electrode showed a capacity of 90 mAh g-1 and the cathode composed of PFcFE4 retained over 90% of the initial capacity after 100 charging-discharging cycles at 10 C. These results demonstrate the great potentials of these ferrocene-containing side-chain polymers as active cathode materials for organic lithium-ion battery applicaitons. Besides, all prepared ferrocene-containing metallopolymers PFcFE1, PFcFE2, PFcFE3 and PFcFE4 also exhibited nonvolatile resistive switching behaviors with the flash memory effect of PFcFE1, PFcFE2 and PFcFE3 as well as the WORM memory feature of PFcFE4, indicating the easily tuned memory properties by changing the chemical structures of the active polymeric backbones. It is also worth noting that the ITO/PFcFE1/Al memory device showed a high ON/OFF current ratio of 103 to 104, a low switch-on voltage of -1.0 V, a long retention time of 1000 s and a large read cycle number up to 105, which is superior to other reported ferrocene-containing memory examples. Chapter 3 focuses on the development of non-conjugated ferrocene-containing copolymers PVFVM1, PVFVM1-1, PVFVM2, PVFVM3, PVFVM4, PVFVM5 and PVFVM6 based on different heteroaromatic moieties which were prepared by AIBN initiated chain addition polymerization. The as-prepared copolymers PVFVM1 and PVFVM1-1 exhibited electrochemical characteristics of both ferrocene and triphenylamine pendants with reversible multiple redox waves at the half potentials of E1/2 = --0.06, 0.30, and 0.42 V (vs. Fc/Fc+). Notably, the composite electrode based on PVFVM1 afforded a discharge capacity of 102 mAh g--1 at 10 C, corresponding to 98% of its theoretical capacity. The cycle endurances of the active polymer electrodes composed of PVFVM1 or PVFVM1-1 were both evaluated for over 50 numbers and no significant capacity reduction over cycles were observed. On the other hand, initial I-V results of memory devices based on PVFVM1, PVFVM1-1, PVFVM2, PVFVM3, PVFVM4 and PVFVM6 also revealed their huge potentials in electronic information storage. The stability and reproducibility of the corresponding memory devices based on these materials will be futher evaluated in the near future. We used 1,1'-ferrocenediboronic acid bis(pinacol) ester to develop conjugated ferrocene-containing main-chain metallopolymers in chapter 4. All these rational designed metallopolymers FcMMP1, FcMMP2, FcMMP3 and FcMMP4 with one or two ferrocene moieties were produced via Suzuki cross-coupling polycondensation. Their structural information, molecular masses, photophysical features and thermal properties have been well studied. Electrochemical performances of the formed polymers were also examined to clarify their potential as cathode-active materials. Other charge-storage characteristics and switching behaviors of these prepared ferrocene-containing main-chain metallopolymers for organic battery and memory applications are under further investigation.

Sodium-ion batteries (SIBs) are considered as a promising alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to the abundance of sodium resource and its low cost. However, the development of anode materials for SIBs to date has been mainly limited to some traditional anodes for LIBs, such as carbonaceous materials. SnSe2 is a member of two dimensional layered transition metal dichalcogenide (TMD) family, which has been predicted to have high theoretical capacity as anode material for sodium ion batteries (756 mAh g-1), thanks to its layered crystal structure. Yet, there have been no studies on using SnSe2 as Na ion battery anode. In this thesis, we developed a simple synthesis method to prepare pure SnSe2 nanosheets, employing N2 saturated NaHSe solution as a new selenium source. The SnSe2 2D sheets achieve theoretical capacity during the first cycle, and a stable and reversible specific capacity of 515 mAh g-1 at 0.1 A g-1 after 100 cycles, with excellent rate performance. Among all of the reported transition metal selenides, our SnSe2 sample has the highest reversible capacity and the best rate performances. A combination of ex-situ high resolution transmission electron microscopy (HRTEM) and X-ray diffraction was used to study the mechanism of sodiation and desodiation process in this SnSe2, and to understand the reason for the excellent results that we have obtained. The analysis indicate that a combination of conversion and alloying reactions take place with SnSe2 anodes during battery operation, which helps to explain the high capacity of SnSe2 anodes for SIBs compared to other binary selenides. Density functional theory was used to elucidate the volume changes taking place in this important 2D material.

Advancements in Li-ion batteries are needed especially for the development of electric vehicles and stationary energy storage. Prior research has shown mesoscale variations in electrode electronic conductive properties, which can cause capacity loss and uneven electrochemical behavior of Li-ion batteries. A micro-four-line probe (μ4LP) was used to measure electronic conductivity and contact resistance over mm-length scales in that prior work. This work describes improvements to overcome the challenge of unreliable surface contact between theμ4LP and the sample. Ultimately a second generation flexible probe called the micro-radial-surface probe (μ4LP) was designed and produced. The test fixture was also optimized to obtain consistent contact with the new measurement probe and to perform measurements at a lower force. The μ4LP was then used to study the effect of heterogeneity on calendering, which is the compression of electrode films to obtain a uniform thickness and desired porosity. The thickness, electronic conductivity and contact resistance of two cathodes and one anode were measured before and after calendering. The the spatial standard deviation divided by the mean was used as a measure of heterogeneity. The results show variability in conductive properties increased for two of the three samples after calendering, despite the increased uniformity in thickness of the electrodes. This suggests that additional quality control metrics are needed besides thickness to be able to identify uneven degradation and produce longer lasting batteries.

Advancements in Li-ion batteries are needed especially for the development of electric vehicles and stationary energy storage. Prior research has shown mesoscale variations in electrode electronic conductive properties, which can cause capacity loss and uneven electrochemical behavior of Li-ion batteries. A micro-four-line probe (μ4LP) was used to measure electronic conductivity and contact resistance over mm-length scales in that prior work. This work describes improvements to overcome the challenge of unreliable surface contact between theμ4LP and the sample. Ultimately a second generation flexible probe called the micro-radial-surface probe (μ4LP) was designed and produced. The test fixture was also optimized to obtain consistent contact with the new measurement probe and to perform measurements at a lower force. The μ4LP was then used to study the effect of heterogeneity on calendering, which is the compression of electrode films to obtain a uniform thickness and desired porosity. The thickness, electronic conductivity and contact resistance of two cathodes and one anode were measured before and after calendering. The the spatial standard deviation divided by the mean was used as a measure of heterogeneity. The results show variability in conductive properties increased for two of the three samples after calendering, despite the increased uniformity in thickness of the electrodes. This suggests that additional quality control metrics are needed besides thickness to be able to identify uneven degradation and produce longer lasting batteries.

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.

Major vehicle manufacturers are committed to expand their electrified vehicle fleet in upcoming years to meet fuel efficiency goals. Understanding the effect of the charge/discharge cycle profiles on battery durability is important to the implementation of batteries in electrified vehicles and to the design of appropriate battery testing protocols. In this work, commercial high-power prismatic lithium ion cells were cycled using a pulse-heavy profile and a simple square-wave profile to investigate the effect of cycle profile on the capacity fade of the battery. The pulse-heavy profile was designed to simulate on-road conditions for a typical hybrid electric vehicle, while the simplified square-wave profile was designed to have the same charge throughput as the pulse-heavy profile, but with lower peak currents. The batteries were cycled until each battery achieved a combined throughput of 100 kAh. Reference Performance Tests were conducted periodically to monitor the state of the batteries through the course of the testing. The results indicate that, for the batteries tested, the capacity fade for the two profiles was very similar and was 11 % ± 0.5 % compared to beginning of life. The change in internal resistance of the batteries over the course of the testing was also monitored and found to increase 21% and 12% compared to beginning of life for the pulse-heavy and square-wave profiles respectively. Cycling tests on coin cells with similar electrode chemistries as well as development of a first principles, physics based model were done in order to understand the underlying cause of the observed degradation. The results from the coin cells and the model suggest that the loss of active material in the electrodes due to the charge transfer process is the primary cause of degradation while the loss of cyclable lithium due to side reactions plays a secondary role. These results also indicate that for high power cells, the capacity degradation associated with the charge-sustaining mode of operation can be studied with relatively simple approximations of complex drive cycles. / Ph. D. / Major vehicle manufacturers are committed to expand their electrified vehicle fleet in upcoming years to meet fuel efficiency goals. Understanding the effect of the charge/discharge cycle profiles on battery durability is important to the implementation of batteries in electrified vehicles and to the design of appropriate battery testing protocols. In this work, commercial lithium ion cells were tested using two profiles with the same energy transfer; a pulse-heavy profile to simulate on-road conditions for a typical hybrid electric vehicle, and a simplified square-wave profile with the same charge flow as the pulse-heavy profile, but with lower currents. Cycling tests on coin cells with similar electrode chemistries as well as development of a first principles, physics based model were done in order to understand the underlying cause of the degradation. The results suggest that the degradation observed is not dependent on the type of profile used. These results also indicate that for high power cells, the capacity degradation associated with the charge-sustaining mode of operation can be studied with relatively simple approximations of complex drive cycles.

In a bid to reduce vehicular emissions, automobile manufacturers are moving towards elec- tric and hybrid vehicles. Most hybrid vehicles use Lithium-ion batteries as energy storage systems. Lithium-ion batteries have a narrow range of temperature within which they can be operated efficiently. Operation of Lithium-ion batteries outside this range decreases the life of batteries and reduces performance of the vehicle. Due to this limitation, it is important to prevent overheating of Lithium-ion batteries. Battery pack studied in this work has a fan system for air-cooling the cells. The battery management system (BMS) in the battery pack functions to keep the temperature of the cells within allowable limits by either regulating the fan speed or communicating with the vehicle controller to adjust magnitude of applied current. BMS used in the work is equipped with limited number of temperature sensors that can measure surface temperature of few cells in the battery pack. Additional temper- ature information can be used for better thermal control of the cells in the battery pack. Lithium-ion cells are known to have a measurable temperature gradient when operating un- der extreme conditions. As a result, the surface temperature of cells as measured by the temperature sensors in BMS is not always representative of the maximum cell temperature. To overcome these limitations, a simplified transient thermal model predicting core and sur- face temperature of cell is presented in this work. This model can be implemented in a BMS for real-time control of cell temperature. The thermal model is validated against data avail- able from testing the battery pack. Different current profiles, representative of real-world driving scenarios, are applied to the thermal model and the temperature rise of cells under those conditions is studied. For an array of cells, the thermal model predicts significant temperature rise along the airflow direction, suggesting the use of last cell temperature for thermal control. For short duration, high magnitude of current pulses, temperature rise is shown to be similar for same thermal energy deposited by different current pulses. The maximum thermal energy that can be deposited in the battery by a current pulse can be determined for given conditions of airflow rate, continuous current and air inlet temperature. The maximum magnitude of thermal energy that can be deposited by a peak current pulse to limit cell temperature is shown to be a function of current magnitude squared and the pulse duration time. For multiple current pulses applied to the battery pack, the model can evaluate the minimum time interval between current pulses to keep the temperature of cells within prescribed limits. The minimum time required between two current pulses is shown to decrease by increasing the airflow rate through the battery pack. By increasing the airflow rate, the battery pack is able to operate at a higher continuous current without exceeding the temperature limit. / Master of Science / In a bid to reduce vehicular emissions, automobile manufacturers are moving towards electric and hybrid vehicles. Most hybrid vehicles have an energy storage system in addition to the conventional Internal Combustion (I.C.) engine. Lithium-ion batteries are used as energy storage systems in most hybrid vehicles due to their high energy density, long life and low self discharge rate. Lithium-ion batteries can be operated efficiently only in a narrow range of temperature. Operating these batteries outside of this temperature range results in their faster degradation which results in lower performance of hybrid vehicle. Due to this limi- tation, prevention of overheating in Lithium-ion batteries is extremely important. To keep the operation of Lithium-ion batteries within specified temperature limits, most batteries in hybrid vehicles are equipped with battery management systems (BMS). The BMS monitors cell voltage, cell temperature and applied current and keeps the temperature of cells within allowable limits. BMS of the battery pack used in this work has fan system for air-cooling the individual cells, and can lower the temperature rise of the cells by varying the fan speed. This BMS has limited temperature sensors that can predict surface temperature of few cells of the battery pack. Additional temperature information can be used to improve thermal control of the battery pack. This work presents a simplified thermal model that can be used in controller of a BMS to improve thermal control of cells and keep the temperature of cells within specified limits.

This thesis investigates several approaches to the development of high-performance batteries. A general background to the field and an introduction to the experimental methods used are given in Chapters 1 and 2 respectively. Chapter 3 presents a study of ordered and disordered LiNi₀.₅Mn₁.₅O₄ materials produced using an optimised resorcinol-formaldehyde gel (R-F gel) synthetic technique. Both materials exhibited good electrochemical properties and minimal side reaction with the electrolyte. Structural analyses of the materials in various states of discharge and charge were undertaken, and from these the charge / discharge processes were elucidated. In chapter 4 R-F gel synthesised Li(Ni₁/₃Mn₁/₃Co₁/₃)O₂ is studied and found to exhibit a high degree of structural stability on cycling, as well as excellent capacity, cyclability and rate capability. Photoelectron spectroscopy studies revealed that the R-F gel derived particles have highly stable surfaces. A discussion of the results and their significance, with particular regard to the outstanding electrochemical performance observed, is also presented. Chapter 5 sets out an investigation into the nature of R-F gel synthesised 0.5Li₂MnO₃:0.5LiNi₁/₃Mn₁/₃Co₁/₃O₂. The electrochemical data revealed that, after an initial activation stage, the R-F gel derived material exhibited a high capacity, good cyclability and exceptional rate capability. This chapter also considers some initial structural investigations and the electrochemical processes occurring on charge. In chapter 6 the use of ether-based electrolytes, combined with various cathode materials, in lithium-oxygen batteries is examined. The formation of decomposition products was observed, and a scheme suggesting probable reaction pathways is given. It was noted that significant quantities of the desired discharge product, lithium peroxide, were formed on the 1st cycle discharge, implying some electrolyte / cathode combinations do demonstrate a degree of stability. A summary of the results and a discussion of their significance are also included.

Energy-storing electrochemical batteries are the most critical components of high energy density storage systems for stationary and mobile applications. Lithium-ion batteries have received considerable interest for hybrid electric vehicles (HEV) because of their high specific energy, but face inherent thermal management challenges that have not been adequately addressed. In the present investigation, a fully coupled electrochemical and thermal model for lithium-ion batteries is developed to investigate the impact of different thermal management strategies on battery performance. This work represents the first ever study of these coupled electrochemical-thermal phenomena in batteries from the electrochemical heat generation all the way to the dynamic heat removal in actual HEV drive cycles. In contrast to previous modeling efforts focused either exclusively on particle electrochemistry on the one hand or overall vehicle simulations on the other, the present work predicts local electrochemical reaction rates using temperature-dependent data on commercially available batteries designed for high rates (C/LiFePO4) in a computationally efficient manner. Simulation results show that conventional external cooling systems for these batteries, which have a low composite thermal conductivity (~1 W/m-K), cause either large temperature rises or internal temperature gradients. Thus, a novel, passive internal cooling system that uses heat removal through liquid-vapor phase change is developed. Although there have been prior investigations of phase change at the microscales, fluid flow at the conditions expected here is not well understood. A first-principles based cooling system performance model is developed and validated experimentally, and is integrated into the coupled electrochemical-thermal model for assessment of performance improvement relative to conventional thermal management strategies. The proposed cooling system passively removes heat almost isothermally with negligible thermal resistances between the heat source and cooling fluid. Thus, the minimization of peak temperatures and gradients within batteries allow increased power and energy densities unencumbered by thermal limitations.