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.

Thesis (Ph.D.) - University of St Andrews, June 2009. / Restricted until 1st June 2011.

Thesis (M.S. in Electrical Engineering)--Naval Postgraduate School, December 2009. / Thesis Advisor(s): Julian, Alexander L. Second Reader: Crisiti, Roberto. "December 2009." Description based on title screen as viewed on January 28, 2010. Author(s) subject terms: Pulsed power, charger, buck converter, field programmable gate array (FPGA), lithium-ion batteries. Includes bibliographical references (p. 77-79). Also available in print.

Thesis (Ph. D.)--Brigham Young University Dept. of Chemical Engineering, 2006. / Includes bibliographical references (p. 155-165).

No description available.

The increased demand for electric vehicles in recent years has driven the development of Li ion battery technology, yielding interesting trends in cathode materials. The layered cathode material Li(Ni1/3Mn1/3Co1/3)O2 gives 30% more reversible lithium extraction than the earlier LiCoO2 and the “overlithiated” material Li(Li0.2Mn0.54Ni0.13Co0.13)O2 gives a semi-reversible capacity 25% higher than Li(Ni1/3Mn1/3Co1/3)O2.1,2 6,7Li MAS NMR and 7Li MATPASS NMR were used to investigate the relation between the lithium ion and metal positions within these materials. It was found that Li(Ni1/3Mn1/3Co1/3)O2 showed a preference for Li ions to associate with Co at high voltages, that Mn4+ and Ni2+ showed some association and that the metals were not highly ordered. Li(Li0.2Mn0.5Ni0.13Co0.13)O2 showed a decrease in transition metal layer lithium upon cycling, in agreement with previous models, an ordering of the metal ions with the reinsertion of the lithium ions and a significant change in structure on deep discharge.3 These results will hopefully lead to more accurate modelling of the materials, understanding of reversibility and to increased reversible capacities in future cathode materials. Additionally work was done to enable high rate in-situ NMR spectra in which spectra are obtained from a cell while cycling in the bore of an NMR spectrometer. A Teflon Swagelok-style cell was designed and the effectiveness of solenoid and saddle coils were tested. It was found that for a 6 mm diameter cathode with a Li metal anode, at least half of the signal intensity could be obtained with a saddle coil whereas the signal was not detected when using a solenoid coil. / Thesis / Master of Science (MSc)

Le développement des véhicules électriques est actuellement en plein essor. Par contre, l’utilisation de ces véhicules est encore limitée en grande partie dû aux problèmes associés à la batterie : coût élevé, faible autonomie, long temps de recharge et durée de vie incertaine. L’influence de la température d’opération sur ces aspects de la batterie est grande et doit être considérée dès les phases initiales de conception de ce type de véhicule. Ce projet présente donc un modèle transitoire du système de gestion thermique d’un véhicule récréatif rechargeable. L’objectif de ce modèle est d’évaluer différentes options et configurations du système de refroidissement afin de minimiser l’impact de la température sur les performances du véhicule.

By replacing the intercalation electrode with a porous electrode and allowing lithium to react directly with O₂ from the air, the new rechargeable Li/O₂ battery system was studied. The porous cathode is comprised of carbon, catalyst and binder. The effect of every component was investigated. The catalyst was believed to play an important role in the performance of the electrode. A number of potential materials have been examined as the catalyst for the O₂ electrode. It suggests that the nature of the catalyst is a key factor controlling the performance of the O₂ electrode. Several catalysts based on first row transition metal oxides each with three different morphologies, bulk, nanoparticulate and mesoporous were studied. The influence of the morphology on the discharge and charge voltage, discharge capacity and cyclability were examined. Among all the catalysts studied, α-MnO₂ nanowires was found to be the best candidate. The reversible capacities of 3000 mAhg⁻¹(normalised by the mass of carbon) or 505 mAhg⁻¹ (based on the total mass of cathode + O₂ ) was obtained. Some of other factors, such as type of carbon, type of binder, type of electrolyte, the construction of cathode and the modification of the catalyst were also investigated, even just in the early stage. Capacity fading during cycling is the main problem in all the cases. A number of experiments were carried out to understand and attempt to avoid the fading problem. After successful synthesis of mesoporous α-Fe₂O₃ with unique properties (by Jiao et al.), the application of these materials in conventional Li battery was studied. Mesoporous α-Fe₂O₃ with ordered walls, mesoporous α-Fe₂O₃ with disordered walls and Fe₂O₃ nanoparticles were examined. It was also applied to examine the different factors that influence the rate of conversion electrodes, i.e., Li⁺ and e⁻ transport to and within the particles, as well as the rate of the two-phase reaction, demonstrating that for this conversion reaction electron transport to and within the particles is paramount.

Hunting for improved energy storage devices based on rechargeable Li-ion batteries and other advanced rechargeable batteries is one of the hottest topics in today's society. Both Li- ion batteries and Li-O2 batteries have been studied within the thesis. The research work of this thesis contains two different parts. Part 1. The controlled synthesis of the extreme small sized nanoparticles and their application for Li-ion batteries; Part 2. The study of the O2 reduction mechanism in Li-O2 batteries with aprotic electrolytes. In the first part, two different types of extremely small-sized TiO2 nanoparticles with at lease on dimension less than 3 nm was synthesised via solvothermal/hydrothermal reaction, i.e., anatase nanosheets and TiO2(B). These nanoparticles were obtained without any contamination of long chain organic surfactants. A series of systematic characterisation methods were employed to analyse the size, phase purity, and surface condition. These extremely small-sized nanoparticles exhibit improved capacity, rate performance as anode materials for Li-ion batteries. The shapes of load curves of charge and discharge are significantly modified due to the reduced size of TiO2 nanoparticles. In chapter 3, we will see the variation of the capacity and the load curve shape of the anatase nanosheets according to their thickness and surface conditions. The origin of the excessive capacity is analysed based on the electrochemical data. It has been identified that both pseudocapacitive (interfacial) Li+ storage and the excessive Li+ -storage from the bulk contribute to the increased capacity. In chapter 4, the shape and size of the sub-3 nm TiO2(B) nanoparticles are studied, a method based the PXRD data is established. These nanoparticles demonstrate a reversible capacity of 221 mAh/g at a rate of 600 mA/g and remain 135 mAh/g at 18000 mA/g without significant capacity fading during cycling. In the last part, a systematic study of O2 reduction mechanism for aprotic Li-O2 batteries based on the combination of a series of electrochemical and spectroscopic data is presented. The novel mechanism unifies two previous models for the growth of Li2O2 during discharge, i.e., Li2O2 particle formation in the solution phase and Li2O2 film formation on the electrode surface. The new mechanism provides fundamental conceptions for the improvement of Li2O2 batteries and shed light on the future research of Li2O2 batteries.

Le domaine du transport aérien est en plein effort de réduction de ses émissions de gaz à effet de serre. Les PEMFC sont sérieusement envisagées afin d'introduire d'avantage d'énergie électrique à bord des avions. On se propose d'étudier la faisabilité de la propulsion d'avions légers alimentés par des systèmes pile à combustible hybridés. On étudie plus spécifiquement un système hybride PEMFC / Batteries Li-Ion produisant un total de 40 kW (20 kW PàC + 20 kW Li-Ion) permettant de propulser un avion léger biplace. Le premier aspect de cette étude est la navigabilité des PEMFC, c'est à dire leur aptitude à fonctionner en milieu aérien. Le second aspect est l'architecture électrique du système hybride, son dimensionnement et son comportement lors de différents profils de vol. Des essais expérimentaux en altitude sont menés et permettent de quantifier la diminution des performances de PàC aérobies liée à la diminution de pression ambiante. Grâce à ces essais et à un modèle numérique de PàC, on compare les technologies aérobies et anaérobies pour différents profils de vol. Un bilan des masses et des volumes associé à chacune de ces deux technologies est dressé. Par ailleurs, des essais en inclinaisons de systèmes PEMFC sont réalisés. L'hybridation directe de PEMFC avec des batteries Lithium est étudiée numériquement et expérimentalement. Un modèle Matlab Simulink de PàC et de batteries Lithium est développé afin de prédire le comportement du système hybride direct et de le dimensionner. Enfin, un banc expérimental d'hybridation directe est réalisé et des essais sont menés, révélant l'intérêt de cette architecture innovante. / The domain of air transport is working at reducing its emissions of greenhouse gases. PEMFC are seriously considered as electrical source for future aircraft. The present study focusses on the feasibility of propulsion of a light aircraft powered by hybridized PEMFC systems. The hybrid PEMFC / Li-Ion batteries system studied here produces 40 kW (20 kW PEMFC + 20 kW Li-Ion) and should be able to power a two-seat light aircraft. The first part of the study is dedicated to PEMFC airworthiness, meaning their capacity to work properly in aeronautical conditions. The second part is dedicated to the hybrid system electrical architecture, its dimensioning and its response to various flight profiles. Aerobic PEMFC performance loss due to drop in ambient pressure is quantified thanks to experiments at various altitude. Thanks to these measurements and to a numerical model, aerobic and anaerobic PEMFC are compared according to various flight profiles. A mass and volume balance of each technology is drawn up. In addition, inclination tests of PEMFC systems are performed. Direct hybridization of PEMFC and Li-Ion batteries is studied numerically and experimentally. A Matlab Simulink model of PEMFC and battery is developed in order to forecast the hybrid system's response and to size it. Finally, an experimental bench is settled up and tests are led, proving the interest of such an innovative architecture.