<p>In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).</p>

Das Ziel der Arbeit bestand darin, die aus der Literatur bekannten Zusammenhänge zwischen Korrosionsaktivität von Stahl im Beton und einer galvanostatischen Pulsmessung, welche unter Laborbedingungen gute Ergebnisse liefern, auf Messungen an realen Bauwerken anzuwenden. Dazu wurden zunächst Untersuchungen an 13 Jahre alten Prüfkörpern durchgeführt und ausgewertet. Die abgeleiteten Zusammenhänge konnten anschließend an realen Bauteilen verifiziert werden. Somit stellt die galvanostatische Pulsmessung eine hilfreiche zerstörungsfreie Prüfmethode zur Interpretation des Korrosionszustandes dar. Die neuen Erkenntnisse lassen eine bessere Einschätzung des Korrosionsverhaltens in Stahlbetonbauwerken zu, als es die Potentialmessung erlaubt.

Magister Scientiae - MSc / In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE). / South Africa

Les piles au lithium tiennent une place importante dans de nombreuses applications, notamment dans le secteur industriel à forte valeur ajoutée. Les oxyfluorures de graphites et graphènes, ainsi que leurs précurseurs oxydes, ont été identifiés comme des matériaux de cathode pouvant permettre d’augmenter la densité d'énergie de ces piles. Durant cette thèse, afin d’obtenir des nouveaux oxyfluorures de graphite, deux voies de synthèse ont été prospectées. Lors de la synthèse enchainant oxydation de Hummers puis fluoration gaz-solide, le paramètre température d’oxydation a été modulé et a donné lieu à des composés contenant des proportions différentes de fonctions oxygénées de type OH, COOH, COC. Lors de la synthèse débutant par la fluoration, différentes méthodes de fluoration ont été mise en oeuvre faisant agir soit le fluor moléculaire soit le fluor radicalaire à deux échelles de synthèse (laboratoire et micropilote). Une caractérisation minutieuse des matériaux issus de chaque voie, croisant les analyses structurales (DRX, ATG, diffusion Raman...) et analyses chimiques (IR, RMN, XPS...) a permis de cerner les modularités sur les effets de structure et de distribution de fonctions à l'échelle locale. Ce panel de composés a été testé en décharge galvanostatique en pile au lithium afin de corréler activité électrochimique des fonctions et gain en performances. / Primary Lithium Batteries are substantial in many applications, particularly in industrial niche sectors. Graphite oxifluorides and their precursors, graphite oxides, are promising materials for the cathodes. We explored two-step synthesis combining Hummers' oxidation and solid-gas fluorination. Temperature of oxidation was key parameter to control OH, COC and COOH ratio. Direct fluorination and controlled fluorination were processed at laboratory and scaled-up. Because of complexity of the materials and specificity at each scale, we cross-checked the data from several techniques for structure (XRD, TGA, Raman spectroscopy...) and chemistry (IR, MAS NMR, XPS...) for an accurate picture. We tested the broad set of materials. Galvanostatic discharges enabled us to understand the electrochemical activity of functions at stake and key factors of design for better performances.

This master's thesis deals with a topic of determination of the most suitable ratio of cathode materials for the lithium-sulfur systems. The first two chapters provide a general introduction to the topic of electrochemical energy sources and present the commonly used primary and secondary battery systems with emphasis on their characteristics and applications. The core of the theoretical part is dedicated to lithium-ion and lithium-sulfur batteries, their working principles along with the benefits or drawbacks related to the particular systems, and widely used materials. The experimental part briefly comments on determining the suitable electrode paste preparation method, the subsequent main part is focused on evaluation of electrochemical performance of cells using different ratios of cathode materials. Five samples of cathode materials were prepared, where the sulfur ratio is in range from 64 to 88 wt. %. Finally, the comparison of all prepared ratios in terms of their electrochemical properties is provided.

This diploma thesis deals with the description of individual types of batteries. The first part is focused to primary and secondary batteries, materials for their positive and negative electrodes with a focus on lithium-ion batteries and their changes over time. The next section focuses on a more detailed description of sodium-ion batteries, used electrode materials and to their problems. Practical part is focesed to preparing of electrode materials and to completing of measuring electrochemical cell and to discribing of measuring methodes and to evaluation of measured data.

The Diploma thesis deals with humic acids and their ability to adsorb metal ions on their surface. Humic acids are aromatic polycyclic compounds which contain carboxylic and fenolic functional groups on their sidechains. Thanks to these functional groups humic acids can form complexes with metal ions of different stability and assist the partial immobilization of pollutants in the nature. In this thesis, the sorption of Pb2+ and Zn2+ ions on humic acids was studied by relatively new electroanalytic method called galvanostatic stripping chronopotentiometry. Experimental data were described by Freundlich and Langmuir isotherms. The results show that the amount of examined metal ions increases with their increasing concentration. Furthermore it was determined that Pb2+ ions are adsorbed better on humic acids than Zn2+ ions. Both metals are adsorbed better from solution containing only one metal ion than in presence of four metals at the same time (Cd, Cu, Zn and Pb) where the sorption of these metals is not influenced by the presence of other metals.

Hlavním cílem této práce je charakterizace vzorků titanátů, jako materiálů pro sodíko-iontové (Na-ion) akumulátory. Syntéza některých vzorků je součástí této práce. Charakterizace je zaměřena na elektrochemické vlastnosti, složení a morfologii použitých materiálů. První část se zabývá lithium-iontovými (Li-ion) akumulátory. Byly vybrány, protože jsou ve vědeckých článcích dobře popsány a základní funkční princip je aplikovatelný také na Na-ion akumulátory. Materiály používáné pro katody, anody a elektrolyty následují po krátké části shrnující parametry a konstrukci Li-ion akumulátorů. Následující kapitola je zaměřena na sodíko-iontové akumulátory. Srovnání sodíku a lithia je následováno materiály používanými pro elektrody a elektrolyty (s důrazem na anodové materiály). Třetí část popisuje analytické metody použité pro charakterizaci elektrod a materiálů. Jedná se o elektrochemickou charakterizaci (cyklická voltametrie a galvanostatické cyklování s potenciálovým omezením), morfologii (rastrovací elektronová mikroskopie) a složení (X-ray difrakční spektroskopie). Poslední dvě kapitoly obsahují syntézu a charakterizaci sodného titanátu a charakterizaci dvou vzorků TiO2. Výsledky této práce jsou shrnuty v závěru.

In a context of an expected increasing use of Lithium-ion batteries in the transportation sector, Volvo AB is developing its own solutions for large electric vehicles. It is then beneficial to reduce the costs, the energy demand and the raw materials demand by improving the battery systems’ performances. For that purpose, understanding the physical phenomena which come into play in lithium ion cells is necessary. This project’s motivation has been to deepen the existing knowledge on one or a group of these phenomena which include those at the origin of the Open Circuit Voltage (OCV) hysteresis. It is characterized by the difference in charging and discharging voltage when the cell is at a resting state. These voltage differences might result in heat losses in the cells. In this thesis, the behaviour of the Open Circuit Voltage (OCV) under different operating conditions is studied, and a Preisach empirical hysteresis model is developed. The core part of the work consisted in experimental measurements of the Open-Circuit-Voltage of 10 Ah prismatic LiFePO4 (Lithium Iron Phosphate) cells. These measurements were completed using the Galvanostatic Intermittent Titration Technique (GITT) that consists of alternative current pulse and relaxation phases. The tests were performed using relaxation times ranging from 1 hour to 48 hours with the cells being under various cycles (series of charge and discharge). The impacts of the temperature, various current rates from 0.1C to 1C (1 A to 10 A) on the OCV and the voltage relaxation were evaluated. The amplitude of the OCV hysteresis that does not vanish after full relaxation, which is defined by the difference between the OCV charge and the OCV after discharge, was found to vary between 5 mV and 20-25 mV depending on the State-of-Charge of the cells. Two peaks are identified around 20-30% and 65-70% State-of-Charge. The measured OCV hysteresis with 24 hours relaxation is about half of the measured OCV hysteresis with 2-5 hours relaxation. The experiments also measured an apparent smaller OCV hysteresis when the magnitude of the current increases; this trend is to be verified after full relaxation. The temperature has an impact on the OCV which is averaging around ±0.2 mV/K. The analysis of the voltage relaxation behaviour described that at low temperatures and low C-Rates, the cells get closer to equilibrium voltage at a slower pace. In addition, a higher test time, characterized by longer relaxation times after each step and/or a larger number of steps within the same State of Charge (SOC) range, tends to increase the time required for the cell to reach an equilibrium. After completing the OCV measurements, a Preisach hysteresis model is developed based on the experimental results. The model predicts the OCV variations of an Lithium ferrophosphate (LFP) cell at ambient temperature when going through various charge and discharge cycles. Its estimated Root Mean Square Error (RMSE) is 3 mV, but the accuracy of the model could be partially confounded with measurement uncertainty. The main outcomes are a more accurate description of the voltage relaxation behaviour and a new estimation of the amplitude of the OCV hysteresis in LFP cells. / I en värld där det finns en förväntad ökning av användandet av litiumjonbatterier inom transportsektorn, utvecklar AB Volvo sina egna lösningar för stora elfordon som lastbilar. För att reducera kostnaderna, energibehovet och efterfrågan på råvaror, är det nödvändigt att förstå fysiska fenomen inom litiumjoncellerna eftersom det kan hjälpa till att förbättra systemens prestanda. Examensarbetets motivation är att fördjupa kunskapen om fenomenen vid uppkomsten av öppen kretsspänningshysteres inom litiumjärnfosfatceller. Denna hysteres definieras av skillnaden mellan öppen kretsspänning (Open-Circuit-Voltage eller OCV) under laddning och OCV under urladdning. Det orsakar över- och underspänning som ökar värmeförlusterna i litiumjoncellerna. Detta projekt studerar beteendet av både spänningsrelaxation och OCV för ett valt intervall av parametrar. Sedan utvecklas en Preisach empirisk modell. Huvuddelen av arbetet bestod i den experimentella mätningen av OCV av 10 Ah prismatiska LiFePO4 celler (Litiumjärnfosfatceller). Dessa experiment genomfördes medelst en mätprocedur som kallas Galvanostatic Intermittent Titration Technique eller Galvanostatisk intermittent titreringsteknik (GITT). Testerna innehåller växelvis strömpuls- och relaxationsfaser. Spänningsrelaxationsfaserna varade mellan 1 och 48 timmar under olika laddnings- och urladdningscykler. Inverkan av båda temperaturen och strömstyrkan (mellan 0.1C och 1C) på OCV utvärderades. Amplituden för OCV hysteresen som kvarstår efter full relaxation beräknades ligga mellan 5 mV och 20-25 mV beroende på cellersladdningstillstånd. Två hysterestoppar identifierades: en runt 70% och en andra mellan 20% och 30% laddningstillstånd. Hysteresen som mäts med 24 timmar av relaxation är runt hälften av hysteresen som mäts med två till fem timmar av relaxation. Med större strömstyrka är den uppmätta hysteresen lite lägre. Ytterligare tester bör göras för att verifiera att hysteresen fortfarande är lägre efter full relaxation. Temperaturen har en begränsad effekt på den totala hysteresen, men entropikoefficientensvärdet är i genomsnitt runt ± 0.2 mV/K. Analysen av relaxations beteende beskriver att en högre temperatur och strömstyrka ökar hastigheten med vilken jämviktspotentialen nås efter strömpulsen. Dessutom orsakaren ökning av den totala testlängden en långsammare relaxering. En längre testtid karaktäriseras av en längre relaxationstid efter varje strömpuls och/eller flera steg för laddningstillstånd. Efter OCV-mätningarna, byggdes en Preisach hysteresmodel med hjälp av de experimentella resultaten. OCV-variationer under olika laddnings och urladdnings cykler modellerades vid rumstemperatur med ett uppskattat minsta kvadratfel på cirka 3 mV. Modellen testades inte med ett begränsat antal cykler så den exakta noggrannheten behöver ytterligare verifieras för att få ner mätosäkerheten. Det huvudsakliga bidraget från detta examensarbete är uppskattning av amplituden för den hysteresen och beskrivningen av spänningsrelaxering efter olika strömpulser, såväl i längd som i amplitud.

Le développement à grande échelle des microbatteries pour des applications diverses comme l’alimentation de secours de certains composants électroniques dans les téléphones portables nécessite une compatibilité avec le procédé de solder-reflow employé dans le domaine de la microélectronique. Dans ce contexte, cette étude porte sur la mise au point d’un nouveau procédé de réalisation de couches minces d’oxysulfures de titane lithiés (LixTiOySz) pour une utilisation en tant qu’électrode positive dans une microbatterie Li-ion. Tout d’abord ce travail a débuté par la synthèse et la caractérisation de plusieurs compositions de sulfures de titane lithiés à l’état massif par réaction en solution de TiS2 ou TiS3 avec le n-butyllithium mais aussi par réaction à l’état solide à haute température entre les précurseurs TiS2, Li2S et Ti. Par la suite, des couches minces de LixTiOySz ont été déposées par pulvérisation cathodique radiofréquence à effet magnétron de cibles réalisées à partir des matériaux lithiés à l’état massif. La composition chimique de ces dépôts dépend de celle de la cible utilisée ce qui permet d’obtenir des couches plus ou moins riches en lithium et en soufre. En revanche, elles sont toutes très mal cristallisées, denses et elles ne présentent pas de structuration particulière. Enfin, les caractérisations électrochimiques des dépôts de LixTiOySz, à la fois en électrolyte liquide et solide, ont permis de mettre en évidence une corrélation entre leur composition chimique et leur comportement électrochimique. Globalement, ces dernières sont performantes, compatibles avec le solder-reflow et donc tout à fait intéressante pour l’application. / Large-scale development of microbatteries for various applications such as back-up power sources for cell phone electronic components needs suitability with reflowing process that is often used in microelectronic. Here we report on the development of a new realization process to produce lithiated titanium oxysulfides (LixTiOySz) thin films for use as positive electrode in Li-ion microbatteries. First of all, this work began with synthesis and characterization of several lithiated titanium sulfides compounds prepared by reaction between TiS2 or TiS3 with n-butyllithium but also by solid state reaction at high temperature between TiS2, Li2S and Ti. Then, LixTiOySz thin films were sputtered by magnetron effect radio-frequency sputtering from targets made of lithiated materials previously synthesized. The chemical composition of those films depends on the target one and allows obtaining thin films with different lithium and sulfur contents. In contrast, they are all amorphous, dense and they don’t have a morphological structuration. Finally, electrochemical characterizations of thin films, both in liquid and solid electrolyte, have highlighted a correlation between their chemical composition and their electrochemical behavior. Taken as a whole, LixTiOySz thin films are powerful, suitable with reflowing process and thus very interesting for the application.