We study some topological properties of dynamical systems. In particular the rela- tionship between spatio-temporal chaotic and Li-Yorke sensitive dynamical systems establishing that for minimal dynamical systems those properties are equivalent. In the same direction we show that being a Li-Yorke sensitive dynamical system implies that the system is also Li-Yorke chaotic. On the other hand we survey the possibility of lifting some topological properties from a given dynamical system (Y, S) to an- other (X, T). After studying some basic facts about topological dynamical systems, we move to the particular case of interval maps. We know that through the knowl- edge of interval maps, f : I → I, precious information about the chaotic behavior of general nonlinear dynamical systems can be obtained. It is also well known that the analysis of the spectrum of time series encloses important material related to the signal itself. In this work we look for possible connections between chaotic dynamical systems and the behavior of its Fourier coefficients. We have found that a natural bridge between these two concepts is given by the total variation of a function and its connection with the topological entropy associated to the n-th iteration, fn(x), of the map. Working in a natural way using the Sobolev spaces Wp,q(I) we show how the Fourier coefficients are related to the chaoticity of interval maps.

A Study on the Feasibility of the Official Appointment of Sub-ward (Li) Chiefs ¡X A Case of Kaohsiung City The purpose of this study was to propose the results of the empirical investigation utilizing the SWOT analysis of the official appointment of sub-ward (Li) chiefs, which revealed the high feasibility of the official appointment. The data germane to this study were disposed through documentary analysis research along with questionnaire survey research and observation research. The subjects of this exploration were categorized into two major groups. One is the public surveyed by telephone resulting in 1017 successful samples; the other is the local officials surveyed by questionnaires including 463 sub-ward (Li) chiefs with a return rate of 74.3% (310), and 271 sub-ward (Li) clerks with a high return rate of 88.2% (239). The results of the survey reveal high credibility which can be seen in chapter three. The results of official appointment were depicted as follows: 1. The advantages of the official appointment: (a) downsizing the administrative organizations, simplifying the administrative procedures, and increasing the effectiveness; (b) slimming down the manpower and cutting down the spending; (c) improving the relationships between the sub-ward (Li) administrative organizations and the community development associations; (d) reducing the expenditures for election and rectifying the vicious election practices; and ; (e) promoting the administrative efficiency without violating democracy. 2. The disadvantages of the official appointment: (a) violating the principles of democracy; (b) violating the principles of local self-governing; (c) increasing the workload after merging the positions of sub-ward (Li) chiefs and clerks; (d) diminishing sub-ward (Li) chiefs¡¦ enthusiasm towards their work; and (e) lowering the functions of community development associations. 3. The reflection of the official appointment: (a) enhancing the local harmony; (b) incurring criticism from the self-benefiting of without-pay elected sub-ward (Li) chiefs¡¦; (c) requesting the government to examine the overlapping functions of sub-ward (Li) chiefs and clerks; and (d) the official appointment of township chiefs becomes the best paradigm of that of sub-ward (Li) chiefs. 4. The threat of the official appointment: (a) accumulating resentment; (b) damaging people¡¦s rights by failing to precisely respond to local situations. Finally, the findings and recommendations of this study were as follows: 1. The author suggests that the government should be more determined to reasonably adjust the boroughs for sub-ward (Li) and village chiefs¡¦ ¡§equal pay for equal work;¡¨ meanwhile, as the number of boroughs decreases, the resistance for official appointment could be reduced and the workload of appointed sub-ward (Li) chiefs would be more even as well. 2. Not only does the official appointment of township chiefs promote administrative efficiency and economizes enormous expenditures, but whose successful experience in reform can be the example for the reform of sub-ward (Li) and village offices. 3. It is believed that appointed sub-ward (Li) chiefs will perform better than elected sub-ward (Li) chiefs. Although there are no existing rules about disciplining elected sub-ward (Li) chiefs, appointed sub-ward (Li) chiefs will be subjected to administrative disciplinary measures or even removed from positions for not fulfilling their duty. Hence, it would be easier to carry out the official appointment of sub-ward (Li) chiefs if borough offices can strengthen sub-ward (Li) chiefs¡¦ functions of reflecting people¡¦s opinions before the cancellation of the sub-ward (Li) chief elections. Key Word¡GSub-ward (Li) Chiefs ¡Bthe Official Appointment of Sub-ward (Li) Chiefs ¡BKaohsiung City ¡Bsurvey research

Les batteries lithium-ion sont présentes dans de nombreuses applications portables ou embarquées car leurs énergies massique et volumique et leur cyclabilité les placent en tête des autres technologies de stockage. Cependant, elles ne résistent pas aux fonctionnements abusifs et peuvent subir des emballements thermiques avec risque d’explosion. Par ailleurs, l’état des composants internes évoluant au cours du vieillissement de la batterie, son comportement en sécurité doit être considéré pour n'importe quel état de santé afin de mieux concevoir la gestion thermique des cellules et du pack batterie. Dans ce contexte, il est donc primordial de comprendre les mécanismes de dégradation de l’ensemble des composants internes d’un élément (matériaux d'électrodes, collecteurs, séparateur et électrolyte) lors d’un vieillissement en fonctionnement normal et le déroulement des évènements en conditions abusives pouvant aboutir à un scénario accidentel.Le séparateur doit alors être considéré comme le premier dispositif de sécurité intrinsèque car il assure la séparation physique entre l’électrode positive et négative. Il doit alors être étudié sur le plan de ses propriétés électrochimiques, mécaniques et thermiques. Pour cela, une méthodologie de caractérisation a été développée, mettant en œuvre un large panel de techniques de caractérisation physique et chimique, et appliquée sur des séparateurs issus de vieillissements en conditions normales et après surcharge. Différentes méthodes de lavage ont permis de discréditer l’évolution morphologique et électrochimique du polymère poreux sans l’interaction des résidus solides associées aux produits de dégradation de l’électrolyte. Ainsi, la porosité et la tortuosité de la matrice polymère, associées à la conductivité ionique du système séparateur/électrolyte, ont été pleinement étudiées.Il a pu être montré que, en accord avec la croissance de la SEI sur l’électrode négative graphite, sa porosité de surface se dégrade avec un encrassement des pores par accumulation de composés solides de la SEI. Aucune conséquence sur les propriétés mécaniques n’a été observée, mais les performances électrochimiques en puissance se dégradent fortement. Une évaluation face aux risques de court-circuit interne par percée dendritique a permis de montrer que la formation de dendrite est favorisée. Le séparateur en tant qu’organe de sécurité face aux risques mécaniques garde donc son efficacité tout au long de la vie de la batterie lithium-ion mais le risque de court-circuit est plus élevé. / Lithium-ion batteries have undeniable assets to meet several of the requirements for embedded applications. They provide high energy density and long cycle life. Nevertheless, they can face irreversible damage during their lives which could cause safety issues like the thermal runaway of the battery and its explosion. It is then essential to understand the degradation mechanisms of all the internal components of an accumulator (i.e. electrode materials, collectors, separator and electrolyte) and the progress of events in abusive conditions that can lead to an accident scenario. The aim of this thesis is to work on the security aspects of Lithium-ion batteries in order to understand these degradation mechanisms and to help to prevent future incidents.Even if the degradation mechanisms of all the internal components are studied in this work, a special attention is given to the separator. This component is indeed one of the most important safety devices of a battery and have to be electrochemically, mechanically and thermally characterized after ageing. Different washing methods have been study in order to characterize the separator without any degradation product of the electrolyte which could interfere. Porosity and tortuosity associated with the ionic conductivity of the separator have been tested.The results show that even if the separator is electrochemically inactive, its porosity can decrease because of the degradation of the negative graphite electrode. Indeed, SEI components obstruct the surface porosity of the separator. This porosity change do not cause any mechanical degradation but decrease separator performances at high current rate and promote lithium dendrite growth.

Les travaux de cette thèse focalisent sur la résolution de deux problèmes majeurs des électrodes positives de systèmes Li-O2, dus à la nature du produit de décharge formé pendant la réaction de réduction de l'oxygène, en milieux Li+ : Lithium peroxyde (Li2O2). Le premier problème est lié au processus de formation de ce dernier (étapes successives de nucléation électrochimiques et de dismutation chimique d'un intermédiaire : le superoxide de lithium), qui conduit à la formation de très grosses particules de peroxyde lithium à la surface de l'électrode. Du fait de leurs taille et de leur résistivité ( le gap du peroxyde de lithium est de 5 eV), il est impossible de recharger de manière efficace et à 100% ce dernier. Cependant, ce problème peut être résolu, grâce à l'ajout d'un additif, qui permet le transport d'électron en solution, et qui peut (en théorie), recharger les particules de Li2O2, détachées de l'électrode. Un très bon candidat a été trouvé dans cette étude, qui a prouvé de très bonne performances pour l'amélioration du processus de recharge, et un effet bénéfique supplémentaire a été caractérisé sur le potentiel de décharge, grâce à un effet catalytique (augmentation du potentiel de réduction de 230 mV). Cependant, cette solution demande de repenser totalement le design actuel des systèmes Li-O2, car ce composé (soluble) peut facilement traverser le séparateur, vers l'électrode de lithium (et causer une autodécharge importante ainsi qu'une boucle de recharge infinie). Le second problème est lié à une autre caractéristique du peroxyde de lithium : sa réactivité. De fait, c'est un base forte au sens de Lewis (en accord avec la théorie HSAB), et réagit de manière importante avec les constituants de l'électrodes (réactivité avec le liant PVDF, mais aussi avec les solvant, le sel et le support carboné de l'électrode). Il est donc nécessaire de trouver un moyen de protéger ce dernier, et une solution proposé dans ce manuscrit a été de réaliser la déposition d'une couche nanométrique de Nb2O5, qui a pour but d'éviter tout contact direct entre le carbone, et le peroxyde de lithium (réaction entre ces deux derniers, qui conduit à la formation d'un composé avec un gap de 7 eV : le carbonate de lithium). Le dépôt fut étudié sur un carbone graphitisé (Zoltek Panex 30) qui, de manière surprenante, a été très résistant versus le peroxyde de lithium. Malheureusement, la présence du dépôt à la surface du tissus n'a pas protégé l'électrode, mais a plutôt eu l'effet inverse, car des traceurs de la formation de carbonate de lithium ont pu être observé (alors qu'aucun traceur n'était détecté sur le tissu nu). Le Nb2O5 a donc été écarté, et d'autres composés doivent être testés dans de futures études, pour cette application. / The present PhD work focuses on solving two major issues of the Li-O2 positive electrodes, both being linked with the nature of the discharge product formed during the Oxygen Reduction Reaction, in Lithium cation electrolyte: Lithium peroxide (Li2O2). The first issue is related to the Discharge mechanism (consecutives Electrochemical nucleation and chemical disproportionation of an intermediate, lithium superoxide), which lead to the formation of large particles of lithium peroxide on the electrode surface. Owing to their size and resistivity (bandgap of lithium peroxide : 5 eV), it is nearly impossible to re-charge efficiently the electrode. This issue can be solved, thanks to the dissolution of an additive in solution, that promote the transport of electrons, and allow the oxidation of large discharge particles (in theory, even the ones disconnected from the electrode). A very good compound was found to efficiently work as a redox shuttle (enhanced Oxygen Evolution reaction), with also a highly beneficial effect for the ORR, with a catalysis effect that allowed to increase the onset of the ORR of 230 mV. However, this solution require a engineering of the practical system as this additive could cross from the positive electrode to the negative side (lithium) and trigger capacity loss and infinite charging loop. The second issue is linked to its reactivity. As a matter of fact, it is an hard base (according to HSAB theory), which reacts readily with a large panel of electrodes component (reactivity toward the PvDf binder, solvent, salts, but also with the carbon material, used as the positive electrode). As such, it is necessary to find a way to protect the latter, and a solution proposed in this work was to use Atomic Layer deposition of Niobium pentoxide (Nb2O5), in order to form a very thin deposit, which was supposed to prevent any contact between the discharge product, and the carbon support (consumption of Carbon, with formation of a large bandgap compound : Lithium carbonate). The deposition was conducted onto a graphitized carbon cloth (Zoltek Panex 30), which surprisingly proved to be highly resistant toward lithium peroxide. Sadly, the presence of the deposit did not protect the electrode but rather made it weaker, with tracers of the formation lithium carbonate. This compound was thus not considered anymore, and others deposits are yet needed to be tested in future studies.

Souza, D. A. Predição e monitoramento da vida útil remanescente de baterias aeronáuticas. 2016. 77f. Dissertação (Mestrado em Engenharia elétrica e da Computação) - Campus de Sobral, Universidade Federal do Ceará, 2016. / Submitted by Programa de Pós-Graduação Engenharia Elétrica e de Computação (secretaria_ppgeec@sobral.ufc.br) on 2017-02-01T16:29:31Z No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2712687 bytes, checksum: ab9342a53c8f7e103c022b0fcec1fcb7 (MD5) / Rejected by Ana Márcia Sousa (marciasousa@ufc.br), reason: Prezada, Favor concluir a submissão. Faltou o preenchimento dos campos: Título em inglês, citação e descrição. Também observamos que o título está todo em maiúsculo e os campos autor e orientador estão preenchidos de forma errada. Favor fazer como no guia de preenchimento, lembrando que apenas os sobrenomes compostos ficam juntos no campo sobrenome. Quanto ao trabalho o aluno precisa corrigir apenas a folha de aprovação de acordo com as normas bibliográficas que se encontram no site da biblioteca on 2017-02-02T12:13:11Z (GMT) / Submitted by Programa de Pós-Graduação Engenharia Elétrica e de Computação (secretaria_ppgeec@sobral.ufc.br) on 2017-02-03T14:01:51Z No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2712687 bytes, checksum: ab9342a53c8f7e103c022b0fcec1fcb7 (MD5) / Rejected by Ana Márcia Sousa (marciasousa@ufc.br), reason: Prezada, Favor verificar os campus: Autor, orientador, citação, descrição e título em inglês e fazer como está no guia de preenchimento que está na documentação enviada a você por ocasião do treinamento. Quanto a dissertação do aluno ainda falta corrigir o alinhamento da pág. de aprovação de acordo com o modelo da Normalização da UFC on 2017-02-03T14:58:11Z (GMT) / Submitted by Programa de Pós-Graduação Engenharia Elétrica e de Computação (secretaria_ppgeec@sobral.ufc.br) on 2017-02-07T15:54:14Z No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2712687 bytes, checksum: ab9342a53c8f7e103c022b0fcec1fcb7 (MD5) / Rejected by Ana Márcia Sousa (marciasousa@ufc.br), reason: Milleani, Infelizmente esta submissão continua incompleta. Por favor, faça com o guia que lhe enviei em mãos, do jeito dos exemplos para não ter que refazer. Ainda falta verificar os campus: Autor (incompleto), orientador (incompleto), descrição (incompleto) Quanto a dissertação do aluno ainda falta corrigir o alinhamento da pág. de aprovação de acordo com o modelo da Normalização da UFC. Você precisa entrar em contato com o aluno e pedir pra ele fazer a substituição do arquivo errado pelo corrigido. Aguardo, Márcia on 2017-02-08T10:46:04Z (GMT) / Submitted by Programa de Pós-Graduação Engenharia Elétrica e de Computação (secretaria_ppgeec@sobral.ufc.br) on 2017-02-08T20:58:04Z No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2711501 bytes, checksum: 89dae5f226ceb6e84f25e57c86aa358f (MD5) / Approved for entry into archive by Ana Márcia Sousa (marciasousa@ufc.br) on 2017-02-09T12:24:59Z (GMT) No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2711501 bytes, checksum: 89dae5f226ceb6e84f25e57c86aa358f (MD5) / Made available in DSpace on 2017-02-09T12:24:59Z (GMT). No. of bitstreams: 1 2017_dis_dadesouza.pdf: 2711501 bytes, checksum: 89dae5f226ceb6e84f25e57c86aa358f (MD5) Previous issue date: 2017-01 / This dissertation presents a proposal for the prediction and monitoring of batteries in UAVs (Unmanned Aerial Vehicles). The applicability of batteries for aeronautical purposes has become quite common due to several advantages over the propellant combustion. However, it is important to use PHM (Prognosis and Health Monitoring) techniques as applied to UAV's equipment, where the Battery Remaining Useful Life (RUL) is supposed to be assessed in this case. This information can be used to aid decision-making on which missions must be assigned to the UAV before the next recharge. This paper presents the algorithms of the Extended Kalman Filter and Particle Filter for predicting Remaining Useful Life of Lithium Polymer (Li-Po) and Lithium Ion (Li-Ion) batteries, which are commonly used in UAVs. The proposed method uses data sets containing the profile of the voltage across the battery over time, where discharge is performed with constant current, current containing white noise, and random current. Several distinct current levels are considered, as an experimental workbench is developed for the test and generation of data sets used in this work. A database provided by NASA is also used for this purpose. The obtained results show that the introduced methodology present good considering the evaluated databases. / Este trabalho apresenta uma proposta para predição e monitoramento de baterias em VANTs (Veículos Aéreos Não Tripulados). A usabilidade de baterias para fins aeronáuticos tem se tornado bastante comum devido a diversas vantagens em relação a propulsores a combustão. Contudo, é importante o uso de técnicas de PMS (Prognóstico e Monitoramento de Saúde) de equipamentos do VANT, sendo que nesse caso deve ser avaliada a Vida Útil Remanescente (RUL- Remaining Useful Life) da bateria. Essa informação pode ser usada para auxiliar à tomada de decisão sobre quais missões são atribuídas ao VANT antes da próxima recarga. O presente trabalho apresenta o algoritmo do Filtro de Kalman Estendido e Filtro de Partículas para predição da Vida Útil Remanescente de baterias de Polímeros de Lítio (Li-Po) e Íons de Lítio (Li-Íon), em que estas são comumente usadas em VANTs. A metodologia proposta utiliza séries de dados contendo a evolução da tensão nos terminais da bateria ao longo do tempo, considerando que a descarga é feita com corrente constante, corrente com ruído branco e corrente aleatória. Diferentes níveis de corrente são considerados, de modo que uma bancada experimental foi desenvolvida para a realização de ensaios e geração das séries de dados usadas neste trabalho. Também foi empregada uma base de dados disponibilizada pela NASA. Os resultados demonstram que a metodologia proposta fornece bons resultados considerando as bases de dados testadas.

Ce travail de thèse, débuté en 2015, a pour but de développer et d'étudier les propriétés de nouveaux liants polymères pour batteries Li-ion. Les synthèses organiques ainsi que leurs caractérisations associées et les tests électrochimiques ont été réalisées à Delft. Puis, des études de spectroscopie photo-électronique par rayons X (XPS) ont été réalisées à Pau pour déterminer et comprendre la réactivité de certain de ces nouveaux matériaux vis-à-vis du lithium. / This PhD work started in 2015, aimed to develop and investigate the properties of new polymers as binders for Li-ion batteries. Organic syntheses with associated characterizations and electrochemical tests were performed in Delft. Then, X-ray photoelectron spectroscopy studies were performed in Pau, to determine and understand the reactivity of some of these new materials toward lithium ions in coin cells.

L'utilisation d'un électrolyte aqueux pour la technologie Li-ion devrait permettre des performances en termes de puissance et de coût tout en garantissant une sécurité de fonctionnement et un impact neutre vis-à-vis de l'environnement. Cette technologie utilise des composés d'insertion du lithium fonctionnant habituellement en milieu organique dont le choix doit être adapté à un électrolyte aqueux, présentant une fenêtre de stabilité électrochimique réduite. Le travail de thèse porte dans un premier temps sur la sélection des différents éléments constituant un accumulateur Li-ion aqueux: choix de l'électrolyte, des collecteurs de courant, des liants d'électrode et des matériaux d'électrode. Les performances électrochimiques en milieu aqueux de différents composés d'insertion du lithium ont été évaluées. Afin d'augmenter la fenêtre de stabilité électrochimique de l'électrolyte aqueux, la passivation des électrodes par réduction de sels de diazonium a été réalisée. L'influence de la nature des sels de diazonium et de l'épaisseur des films sur les performances électrochimiques des électrodes a été évaluée par diverses techniques, voltampérométrie et impédance électrochimique. Les résultats obtenus montrent l'impact positif des dépôts obtenus vis-à-vis de l'augmentation de la surtension de réduction de l'eau. Ces travaux ouvrent la voie à des perspectives prometteuses sur cette technologie Li-Ion aqueuse. / The use of aqueous electrolytes should permit to improve power performances and decrease significantly the battery cost. Moreover, these kind of electrolytes guarantee a safely use with reduced consequence on the environment. This technology use active materials enable to inserted and deinserted lithium ion. But the choice of lithium insertion compounds was guided and limited by the water electrochemical stability. We selected each component of the Li-ion cell which could be used in aqueous electrolyte; the lithium salt, the binder and the active material. The electrochemical performances of several active materials in aqueous electrolyte were evaluated. In order to increase the Li-ion cell tension, a passive film was form on the electrode surface by diazonium salt reduction. Influence of molecule design and film thickness were studied by voltammetry and electrochemical impedance spectroscopy. The results clearly show the interest of the formation of these films for lowering the reduction potential of water on glassy carbon and practical Li-ion electrode. This study opens very promising route for the aqueous lithium batteries.

The electrolyte is a crucial part of any lithium battery, strongly affecting longevity and safety. It has to survive rather severe conditions, not the least at the electrode/electrolyte interfaces. Current commercial electrolytes based on 1 M LiPF 6 in a mixture of organic solvents balance the requirements on conductivity and electrochemical stability, but they are volatile and degrade when operated at temperatures above ca. 70°C. The salt could potentially be replaced with e.g. LiTFSI, but corrosion of the aluminium current collector is an issue. Replacing the graphite negative electrode by Li metal for large gains in energy density challenges the electrolyte further by exposing it to freshly deposited Li, leading to poor coulombic efficiency (CE) and consumption of both Li and electrolyte. Highly concentrated electrolytes (up to > 4 M) have emerged as a possible remedy, by a changed solvation structure such that all solvent molecules are coordinated to cations – leading to a lowered volatility and melting point, an increased charge carrier density and electrochemical stability, but a higher viscosity and a lower ionic conductivity. Here two approaches to highly concentrated electrolytes are evaluated. First, LiTFSI and acetonitrile electrolytes with respect to increased electrochemical stability and in particular the passivating solid electrolyte interphase (SEI) on the anode is studied using electrochemical techniques and X-ray photoelectron spectroscopy. Second, lowering the liquidus temperature by high salt concentration is utilized to create an electrolyte solely of LiTFSI and ethylene carbonate, tested for application in Li metal batteries by characterizing the morphology of plated Li using scanning electron microscopy and the CE by galvanostatic polarization. While the first approach shows dramatic improvements, the inherent weaknesses cannot be completely avoided, the second approach provides some promising cycling results for Li metal based cells. This points towards further investigations of the SEI, and possibly long-term safe cycling of Li metal anodes. / Elektrolyten är en fundamental del av ett litiumbatteri som starkt påverkar livslängden och säkerheten. Den måste utstå svåra förhållanden, inte minst vid gränsytan mot elektroderna. Dagens kommersiella elektrolyter är baserade på 1 M LiPF 6 i en blandning av organiska lösningsmedel. De balanserar kraven på elektrokemisk stabilitet och jonledningsförmåga, men de är lättflyktiga och bryts ned när de används vid temperaturer över ca. 70°C. Saltet skulle kunna bytas ut mot t.ex. LiTFSI, vilket ökar värmetåligheten avsevärt, men istället uppstår problem med korrosion på den strömsamlare av aluminium som används för katoden. Genom att byta ut grafitanoden i ett Li-jonbatteri mot en folie av litiummetall kan man öka energitätheten, men då litium pläteras bildas ständigt nya Li-ytor som kan reagera med elektrolyten. Detta leder till en låg coulombisk effektivitet genom nedbrytning av både Li och elektrolyt. Högkoncentrerade elektrolyter har en mycket hög saltkoncentration, ofta över 4 M, och har lags fram som en möjlig lösning på många av de problem som plågar denna och nästa generations batterier. Dessa elektrolyter har en annorlunda lösningsstruktur, sådan att alla lösningsmedelsmolekyler koordinerar till katjoner – vilket leder till att de blir mindre lättflyktiga, får en ökad täthet av laddningsbärare, och en ökad elektrokemisk stabilitet. Samtidigt får de en högre viskositet och lägre jonledningsförmåga. Här har två angreppssätt för högkoncentrerade elektrolyter utvärderats. I det första har acetonitril, som har begränsad elektrokemisk stabilitet och ett högt ångtryck, blandats med LiTFSI för en uppsättning av elektrolyter med varierande koncentration. Dessa har testats i Li-jonbatterier och i synnerhet den passiverande ytan på grafitelektroder har undersökts med både röntgen-fotoelektronspektroskopi (XPS) och elektrokemiska metoder. En markant förbättring av den elektrokemiska stabiliteten observeras, men de inneboende bristerna hos elektrolyten kan inte kompenseras fullständigt, vilket skapar tvivel på hur väl detta kan fungera i en kommersiell cell. Med det andra angreppssättet har hög saltkoncentration nyttjats för sänka smältpunkten för en elektrolyt baserad på etylenkarbonat, som annars inte kan används som enda lösningsmedel. Dessa elektrolyter har testats för användning i Limetall-batterier genom långtidstest, mätning av den coulombiska effektiviteten och analys av deponerade Li-ytor med svepelektronmikroskop. Resultaten är lovande, med över 250 cykler på 0.5 mAh/cm2 och en effektivitet på över 94%, men framförallt observeras en mycket jämnare deponerad Li-yta, vilket kan möjliggöra säker cykling av Li-metall-batterier. Ett logiskt nästa steg är studier av Liytan med t.ex. XPS för att utröna vad som skiljer den från ytan som bildats i en 1 M referenselektrolyt.

La voie hydrométallugique représente une alternative pour la récupération des métaux de valeur tels que le nickel et le cobalt contenus dans les batteries Li-ion usagées. La première étape du procédé hydrométallurgique, l'étape de lixiviation a été optimisée grâce à l'étude du comportement du matériau actif d'électrode positive LiNi1/3Mn1/3Co1/3O2 (NMC) qui s'avère être le candidat idéal pour les batteries de véhicules électriques. Tout d'abord, l'étude des aspects thermodynamiques de la réaction de dissolution a permis de prédire le comportement du NMC dans divers acides. Puis, l'approche cinétique a conduit à l'élucidation du mécanisme se produisant lors de l'étape de lixiviation et à la mise en évidence de l'étape cinétiquement déterminante de la dissolution. Ce mécanisme a par la suite été généralisé aux autres matériaux couramment rencontrés dans les batteries Li-ion. L'impact d'agents réducteurs minéraux, organiques et métalliques pour promouvoir la dissolution du NMC a été évalué. Cette approche compare l'effet de réactifs à faible (acides sulfurique et chlorhydrique) et fort (acides citrique, oxalique et formique et peroxyde d'hydrogène) pouvoir réducteur ainsi que celui du cuivre et de l'aluminium provenant des collecteurs de courants des batteries Li-ion. Cette étude soulève le fort intérêt de l'emploi des collecteurs de courant présents de manière inhérente dans la fraction traitée par hydrométallurgie. / Basic hydrometallurgical routes represent an alternative to recover valuable metals such as nickel and cobalt from spent Li-ion batteries. The first step of hydrometallurgical process, lixiviation step is optimized by studying the behaviour of LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrode active material, due to its good performances which make it an adequate candidate for the electric vehicles. First of all, the study of thermodynamic aspects allows predicting the behaviour of NMC material in various acidic media. Then, the kinetic approach leads to define the mechanism occurring during the leaching step and to outline the rate-limiting step of the dissolution. The reductive effect of mineral, organic and metallic reducing agents to promote leaching of NMC material is evaluated. The approach comparatively evaluates the reducing power impact of weak (sulfuric and hydrochloric acids), strong reducing agents (citric, oxalic and formic acids and hydrogen peroxide) and copper and aluminum from Li-ion batteries current collectors. This work points out the strong interest to advantageously use current collectors inherently present in the fraction treated by hydrometallurgy.

Les accumulateurs Li-ion sont des systèmes de stockage électrochimique de l’énergie composés de deux électrodes, dans lesquelles les ions Li+ vont venir s’insérer réversiblement lors des cycles de charge et de décharge. Afin d’intégrer le domaine des véhicules électriques, leur densité d’énergie doit être augmentée pour apporter l’autonomie demandée. Ceci peut être réalisé en augmentant la d.d.p. entre les deux électrodes. Nous visons ici la synthèse de nouveaux matériaux polyanioniques d’électrode positive dans lesquels le lithium pourrait venir s’insérer à haut potentiel en faisant intervenir le couple Cu3+/Cu2+ (5,3 V vs Li+/Li). Parmi les phosphates de cuivre synthétisés, Li2CuP2O7 présente une oxydation non réversible à haut potentiel (> 5 V). Sa synthèse à basse température permet d’exacerber les réactions, en raison de la faible taille des particules obtenues ainsi que de la présence de carbone conducteur à leur surface, mais la phase s’avère instable à haut potentiel.En ce qui concerne les composés de type sulfate, une nouvelle phase Li4Cu4O2(SO4)4 est isolée, montrant une insertion réversible du lithium à une valeur moyenne de 4,7 V. Cependant, la capacité de ce matériau est très faible (15 mAh.g-1) et plusieurs substitutions chimiques avec du fluor, du magnésium ou du sodium sont étudiées dans le but d’augmenter la mobilité du lithium. / Li-ion batteries (LIBs) are energy storing electrochemical devices composed of two electrodes, in which Li+ ions are reversibly inserted during charge and discharge cycles. Their use in electric vehicles relies on the increase of their energy density, to provide enough autonomy. This can be reached by increasing the cell d.d.p. We thus aim the synthesis of new positive electrode polyanionic materials, in which lithium could be inserted at high potential, using the Cu3+/Cu2+ couple’s activity (5,3 V vs Li+/Li). Among the synthesized copper phosphates, Li2CuP2O7 presents a non-reversible oxidation at high potential (>5 V). Its low temperature synthesis intensifies the reaction, due to the smaller particle size achieved as well as the presence of a conductive carbon coating, but the phase is instable at high potential. Concerning sulfate-type compounds, a new phase Li4Cu4O2(SO4)4 is isolated, showing a reversible lithium insertion at an average value of 4.7 V. Nevertheless, its capacity is very low (15 mAh.g-1) and various chemical substitutions with fluorine, magnesium or sodium are attempted to increase lithium’s mobility.