En raison de l'augmentation de la demande d'énergie, ressources écologiques respectueux de l'environnement et durables (solaires, éoliennes) doivent être développées afin de remplacer les combustibles fossiles. Ces sources d'énergie sont discontinues, étant corrélés avec les conditions météorologiques et leur disponibilité est fluctuant dans le temps. En conséquence, les dispositifs de stockage d'énergie à grande échelle sont devenus incontournables, pour stocker l'énergie sur des échelles de temps longues avec une bonne compatibilité environnementale. La conversion d'énergie électrochimique est le mécanisme clé pour les développements technologiques des sources d'énergie alternatives. Parmi ces systèmes, les batteries Lithium-ion (LIB) ont démontré être les plus robustes et efficaces et sont devenus la technologie courante pour les systèmes de stockage d'énergie de haute performance. Ils sont largement utilisés comme sources d'énergie primaire pour des applications populaires (ordinateurs portables, téléphones cellulaires, et autres). La LIB typique est constitué de deux électrodes, séparés par un électrolyte. Celui-ci joue un rôle très important dans le transfert des ions entre les électrodes fournissant la courante électrique. Ce travail de thèse porte sur les matériaux complexes utilisés comme électrolytes dans les LIB, qui ont un impact sur les propriétés de transport du ion Li et les performances électrochimiques. Habituellement l'électrolyte est constitué de sels de Li et de mélanges de solvants organiques, tels que les carbonates cycliques ou linéaires. Il est donc indispensable de clarifier les propriétés structurelles les plus importantes, et leurs implications sur le transport des ions Li+ dans des solvants purs et mixtes. Nous avons effectué une étude théorique basée sur la théorie du fonctionnelle densité (DFT) et la dynamique moléculaire (MD), et nous avons consideré des carbonates cyclique (carbonate d'éthylène, EC, et carbonate de propylène, PC) et le carbonate de diméthyle, DMC, linéaire. Les calculs DFT ont fourni une image détaillée des structures optimisées de molécules de carbonate et le ion Li+, y compris les groupes pures Li+(S)n (S =EC,PC,DMC et n=1-5), groupes mixtes binaires, Li+(S1)m(S2)n (S1,S2=EC,PC,DMC, m+n=4), et ternaires Li+(EC)l(DMC)m(PC)n (l+m+n=4). L'effet de l'anion PF6 a également été étudié. Nous avons aussi étudié la structure de la couche de coordination autour du Li+, dans tous les cas. Nos résultats montrent que les complexes Li+(EC)4, Li+(DMC)4 et Li+(PC)3 sont les plus stables, selon les valeurs de l'énergie libre de Gibbs, en accord avec les études précédentes. Les énergies libres de réactions calculés pour les mélanges binaires suggèrent que l'ajout de molécules EC et PC aux clusters Li+ -DMC sont plus favorables que l'addition de DMC aux amas Li+-EC et Li+-PC. Dans la plupart des cas, la substitution de solvant aux mélanges binaires sont défavorables. Dans le cas de mélanges ternaires, la molécule DMC ne peut pas remplacer EC et PC, tandis que PC peut facilement remplacer EC et DMC. Notre étude montre que PC tend à substituer EC dans la couche de solvation. Nous avons complété nos études ab-initio par des simulations MD d'une ion Li immergé dans les solvants purs et dans des mélanges de solvants d'intérêt pour les batteries, EC:DMC(1: 1) et EC:DMC:PC(1:1:3). MD est un outil très puissant et nous a permis de clarifier la pertinence des structures découvertes par DFT lorsque le ion est entouré par des solvants mélangés. En effet,la DFT fournit des informations sur les structures les plus stables de groupes isolés, mais aucune information sur leur stabilité ou de la multiplicité (entropie) lorsqu'il est immergé dans un environnement solvant infinie. Les données MD, ainsi que les calculs DFT nous ont permis de donner une image très complète de la structure locale de mélanges de solvants autour le ion lithium, sensiblement amélioré par rapport aux travaux précédents. / Due to the increasing global energy demand, eco-friendly and sustainable green resources including solar, or wind energies must be developed, in order to replace fossil fuels. These sources of energy are unfortunately discontinuous, being correlated with weather conditions and their availability is therefore strongly fluctuating in time. As a consequence, large-scale energy storage devices have become fundamental, to store energy on long time scales with a good environmental compatibility. Electrochemical energy conversion is the key mechanism for alternative power sources technological developments. Among these systems, Lithium-ion (Li+) batteries (LIBs) have demonstrated to be the most robust and efficient, and have become the prevalent technology for high-performance energy storage systems. These are widely used as the main energy source for popular applications, including laptops, cell phones and other electronic devices. The typical LIB consists of two (negative and positive) electrodes, separated by an electrolyte. This plays a very important role, transferring ions between the electrodes, therefore providing the electrical current. This thesis work focuses on the complex materials used as electrolytes in LIBs, which impact Li-ion transport properties, power densities and electrochemical performances. Usually, the electrolyte consists of Li-salts and mixtures of organic solvents, such as cyclic or linear carbonates. It is therefore indispensable to shed light on the most important structural (coordination) properties, and their implications on transport behaviour of Li+ ion in pure and mixed solvent compositions. We have performed a theoretical investigation based on combined density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulations, and have focused on three carbonates, cyclic ethylene carbonate (EC) and propylene carbonate (PC), and linear dimethyl carbonate (DMC). DFT calculations have provided a detailed picture for the optimized structures of isolated carbonate molecules and Li+ ion, including pure clusters Li+(S)n (S=EC, PC, DMC and n=1-5), mixed binary clusters, Li+(S1)m(S2)n (S1, S2 =EC, PC, DMC, with m+n=4), and ternary clusters Li+(EC)l(DMC)m(PC)n with l+m+n=4. Pure solvent clusters were also studied including the effect of PF6- anion. We have investigated in details the structure of the coordination shell around Li+ for all cases. Our results show that clusters such as Li+(EC)4, Li+(DMC)4 and Li+(PC)3 are the most stable, according to Gibbs free energy values, in agreement with previous experimental and theoretical studies. The calculated Gibbs free energies of reactions in binary mixtures suggest that the addition of EC and PC molecules to the Li+-DMC clusters are more favourable than the addition of DMC to Li+-EC and Li+-PC clusters. In most of the cases, the substitution of solvent to binary mixtures are unfavourable. In the case of ternary mixtures, the DMC molecule cannot replace EC and PC, while PC can easily substitute both EC and DMC molecules. Our study shows that PC tends to substitute EC in the solvation shell. We have complemented our ab-initio studies by MD simulations of a Li-ion when immersed in the pure solvents and in particular solvents mixtures of interest for batteries applications, e.g. , EC:DMC (1:1) and EC:DMC:PC(1:1:3). MD is a very powerful tool and has allowed us to clarify the relevance of the cluster structures discovered by DFT when the ion is surrounded by bulk solvents. Indeed, DFT provides information about the most stable structures of isolated clusters but no information about their stability or multiplicity (entropy) when immersed in an infinite solvent environment. The MD data, together the DFT calculations have allowed us to give a very comprehensive picture of the local structure of solvent mixtures around Lithium ion, which substantially improve over previous work.

This thesis reports exploratory studies on the synthesis and characterisation of new compounds as cathode materials for second generation sodium batteries, with a particular emphasis on preparing new iron-phosphite and molybdenum oxyfluoride cathode materials. Seven different compounds are hereby reported: the sodium iron fluoro-phosphite of formula NaFe₃(HPO₃)₂[(H,F)PO₂OH)₆], the iron-phosphite Fe₂(HPO₃)₃, the sodium iron-phosphite NaFe(H₂PO₃)₄, the sodium iron phosphate NaFe(HPO₄)(H₂PO₄)₂·H₂O and three molybdenum oxyfluoride compounds of formula Na₂MoO₂F₄, KNaMoO₂F₄ and KMoO₂F₃. The synthesis of these compounds was performed by hydrothermal and solvothermal methods at temperatures ranging from 100 °C to 160 °C. The compounds were then fully characterised using the following techniques: single crystal X-ray diffraction (SXD), powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), elemental analysis (EA), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and electrochemical testing. Magnetic properties have also been studied where appropriate.

published_or_final_version / abstract / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

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Green technologies have recently gained interest for many reasons. Economic factors in conjunction with an increased social desire to reduce our environmental impact on the Earth have created a desire for more environmentally friendly technologies, especially automotive technologies such as the electric car. While public interest in electric vehicles is growing, there are a number of challenges which must first be addressed before their widespread adoption is possible. Cost, longevity, and range are all important factors which need to be addressed for electric vehicles to compete directly with their gasoline counterparts. By more efficiently using the energy stored within the battery pack, some of these issues can be addressed. This study focuses on the thermal management systems for electric vehicles and the application of design optimization in the early design phase considering the pack in its entirety. A liquid cooling system is considered for a current generation electric vehicle, with time dependent heat generation rates within the battery cells based on vehicle operating conditions. Identifying the most efficient distribution of cooling within the battery pack to achieve uniform temperature is the objective of optimization. Simulations were performed on a complete battery pack model, featuring 288 battery cells and 144 cooling plates. Anisotropic material properties and non-uniform heat generation rates are included as well as energy demands based on a representative vehicle drive cycle. Results have shown that through design optimization, the standard deviation of temperature within the battery cells can be improved by as much as 80% when compared to a conventional design. The standard deviation of temperature saw improvement from an average of 0.2828 K for a conventional design to 0.05318 K after optimization. These results are specific to the given battery pack construction, battery cell, and cooling type. The method of modeling and analysis can be extended to many battery geometries and cooling technologies in the future. Application of design optimization to the problem of thermal iii management system design can yield significant improvements to battery pack thermal management, and thereby incrementally improve the efficiency of electrified vehicles. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2013-10-30 10:49:28.639

Orientador: Mirian Cristina dos Santos / Banca: Marcia Regina de Moura Aouada / Banca: Silmara Rossana Bianchi / Resumo: Neste trabalho foram desenvolvidos métodos de análise aplicados a baterias e pilhas. A primeira etapa do trabalho consistiu na caracterização do material ativo das amostras de baterias e pilhas. Com a Microscopia Eletrônica de Varredura (MEV) e Espectroscopia de Dispersão de Energia (EDS), foi possível calcular o tamanho médio das partículas com variação de 8,08 a 22,96 μm e verificar a presença dos metais tóxicos como Cd, Cr e Ni. O Cd apenas foi encontrado na bateria de Níquel- Cádmio (NiCd) e os demais elementos potencialmente tóxicos (Cr, Pb, As e Hg) não foram detectados. Ainda para a caracterização do material ativo das amostras e com auxílio da Difratometria de Raios-X (DRX) foi possível identificar a presença dos compostos químicos. Ensaio de lixiviação foi realizado para promover a extração dos metais tóxicos presentes no material ativo das baterias e pilhas. Os lixiviados foram analisados por Espectrometria de Absorção Atômica em Chama (FAAS) e Espectrometria de Emissão Óptica com Plasma Acoplado Indutivamente (ICP OES) para a quantificação dos metais Cr, Cd, Ni e Pb. O procedimento utilizado para promover as extrações foi ABNT NBR 10.005/2004 que permitiu avaliar a toxicidade do resíduo sólido. Os resultados obtidos através das duas técnicas utilizadas foram concordantes entre si, com a aplicação do Test t de Student com 95% de confiança e se mostraram adequadas para a determinação dos analitos de interesse no extrato lixiviado. A bateria NiCd apresentou uma alta concentração de Cd em sua composição e foi considerada um resíduo tóxico segundo a NBR 10.005/2004. Para a determinação total dos analitos na amostra de bateria NiCd, foi desenvolvido um procedimento de preparo de amostra que permitiu a total digestão da mesma, visando à quantificação dos metais tóxicos por ICP OES. O procedimento B se mostrou mais adequado para promover a... / Abstract: In this work analytical methods applied to batteries were developed. The first stage work consisted in the characterization of the active material of the samples and batteries. With Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) it was possible to calculate the mean particle size with a range from 8.08 to 22.96 μm and verifying the presence of toxic metals such as Cd, Cr and Ni. The Cd was found only in the nickel-cadmium - NiCd batteries only, the other potentially toxic elements (Cd, Cr, Pb, As and Hg) were not detected. For the characterization of active material and the samples with the aid of X- Ray Diffraction (XRD) it was possible to identify the presence of chemical compounds. Leaching test was conducted to promote the extraction of toxic metals present in the active material of batteries. The leachates were analyzed by Flame Atomic Absorption Spectrometry (FAAS) and Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) for the quantification of metals Cr, Cd, Ni and Pb. The procedure used to promote the extractions was the ABNT NBR 10.005/2004 devised for evaluating the toxicity of solid waste. The results obtained by the two techniques were concordant between themselves, with the application of the Student's t-test with 95% confidence level and were adequate for the determination of the analytes in the leachate extract. The NiCd battery showed a high concentration of Cd in its composition and was considered a toxic waste according to NBR 10.005/2004. For total determination of the analytes in the NiCd sample, a procedure for sample preparation was developed that resulted in complete digestion of the same in order to quantify the toxic metals by ICP OES. Procedure B was more suitable to promote digestion of the samples with the determination of Cr, Cd, Ni and Pb. The accuracy using procedure B was evaluated using the NiCd battery and the ... / Mestre

The high-performance sodium metal chloride battery has garnered significant interest in the past decade due to its multiple advantages such as high energy density, deep discharge cycling ability, high safety level, 100% coulombic efficiency, and a broad ambient-temperature operating range. Current development of the sodium-metal chloride batteries is focused on improving its performance and cycling life. This work investigates micro-scale mass transfer and kinetic parameters, which is related to cell performance, for building a complete model. In a typical commercial sodium metal chloride cell, there is mass transfer and conduction throughout the thick positive electrode. The electrode materials participate in redox reactions neither homogeneously nor simultaneously. Therefore, a much thinner positive electrode is introduced in this work in order to remove added macro-scale effects in the electrode from the measurement. Therefore, the number of parameters needed to describe the data was reduced because the experimental design minimizes spatial variations within the cell. Chapter 2 discusses the impact of iron addition to a sodium nickel-chloride cell by investigating ionic transport within the metal chloride phase. The electrochemical performance of a sodium mixed-metal (Ni, Fe) halide cell is characterized for different cathode compositions and at different rates. Charge/discharge data are characterized by a smaller nickel-voltage plateau during discharge than during charge, indicating that some of the NiCl₂ reduces at cell potentials nominally associated with the iron plateau. One means of describing the difference between charge and discharge is to consider transport processes within the mixed NiCl₂/FeCl₂ solid phase. A one-dimensional model has been used to simulate the ionic transport within the (Ni,Fe)Cl₂ phase; the transport model predicts the ratio of discharge to charge iron plateaus reasonably well for most rates and compositions. In order to further investigate complex dynamic behavior of the open-circuit potential (OCP) and galvanic interactions in an iron-doped sodium nickel-chloride cell, a GITT (Galvanostatic Intermittent Titration Technique) method is used in Chapter 3. The response to open-circuit interrupts of porous mixed iron-nickel cathodes has been characterized as a function of state of charge (SOC) for different iron loadings and different charge and discharge rates. After discharge, OCP can evolve in time from the iron plateau to the nickel plateau, and this behavior can be explained by galvanic interactions between iron metal and Ni²⁺. Characteristic times of the OCP transients depend on SOC and can be large. When the OCP has converged on a steady state during discharge, its value may provide an estimate of the mole fraction of NiCl₂ at the interface of the triclinic (Ni,Fe)Cl₂ film that resulted from metal oxidation. Sulfur-containing additives were shown to have dramatic impact on cell resistance and performance. In Chapter 4, the electrochemistry of iron sulfide in nickel/iron porous electrodes in molten sodium tetrachloroaluminate electrolyte was investigated. With the addition of FeS to the electrolyte, results indicate the formation of nickel sulfide species on the metal electrode and an increasing discharge capacity with increasing amount of iron sulfide. The cathode with highest sulfide content appears to be highly resistive. Galvanostatic interrupt experiments shows complex dynamic behavior of sulfide-iron-NiCl₂ galvanic interactions. With a goal of extending knowledge of kinetic and mass transfer parameters for understanding mass transfer, Chapter 5 discusses the performance of nickel/iron cells for a broader range of temperature, composition and current. The experiments were tested at different temperatures. Also, three granule compositions with different iron levels are tested at four different current rates. The data from this study can be for use in a complete model of the sodium-nickel/iron chloride cell and in the optimization of the electrode. In the previous chapters, a thinner positive electrode is used in order to remove the effects of macro-scale mass transfer. Chapter 6 discusses the impact of thickness of the cathode on the mass macro-scale transfer and conduction within the metal chloride and metal phase. The goal is to improve modeling of tortuosity as a function of state of charge because transport is important in real systems, and modeling ohmic resistance, for example, can be challenging.

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