<p>The widespread commercialization of electric vehicles is currently hindered by their inability to compete with conventional gasoline-powered vehicles in terms of refueling time. The main barrier to achieving fast charge of lithium-ion batteries is the plating of metallic lithium on the surface of the graphite negative electrode, which is known to occur most prevalently at high C-rates, low temperatures, and high states of charge (SOC). While it is accepted that the lithium plating process is largely reversible, the factors affecting the reversibility of lithium plating have not been thoroughly investigated. This work seeks to determine the most influential factors affecting the reversibility of lithium plating in order to devise strategies to mitigate long-term damage to the cell if lithium plating has been detected. It was determined that the temperature during the rest phase following plating has the most significant influence on plating reversibility, with cells undergoing rest at 30 ℃ exhibiting nearly twice the Coulombic inefficiency of cells undergoing rest at 0 ℃. Additionally, a novel technique was developed to observe the relaxation processes directly in a graphite electrode just after lithium plating has occurred. The occurrence of electrochemical stripping and the dissolution of overshooting phases in graphite were verified through direct <i>in-situ</i> observation. A two-part model is presented to describe the progression of the relaxation processes in graphite after lithium plating occurs under high rate operation.</p>

Degradation behavior of commercial lithium-ion pouch cells containing LiCoO2 cathode and graphite anode was investigated for a cycling under continuous overcharge condition. This condition is frequently experienced in electric vehicles in an event of Battery Management System (BMS) failure. Failure of BMS results in an unbalanced module further resulting in overcharging or overdischarging the cells. Commercial cells with 5Ah capacity were continuously cycled at different upper cutoff voltages and 1C-rate to develop a better understanding of the overcharge process. The results show that as the upper cutoff voltage is extended, the cell gains a higher initial capacity. However, the cycle life of the cell diminishes significantly. The extent of overcharge was found to be an important parameter not only for the electrochemical performance but also for cell integrity. Cells overcharged beyond 4.5 V had a significant volume increase and a rapid increase in the capacity fade. The cell starts to swell at this stage and a considerable increase in the temperature and internal resistance of the cells is observed. Thermal imaging of the cell revealed non-uniform temperature distribution and localized degradation sites were identified. Evidence of lithium plating and electrolyte deposits on anode was observed in cells charged beyond 4.4 V, with SEM-EDS verifying their presence. A comparative study of various State of Health (SoH) estimation parameters is presented and the proposed parameter Φ_R based on internal resistance measurement is found to be a good indicator of aggravated degradation in cells.<br>

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In diesem Beitrag wird ein neuer Ansatz zur Modellierung von Lithium-Ionen-Zellen vorgestellt, bei dem neben einem Modell zur Beschreibung des Nominalverhaltens der Zelle ein Unbestimmtheitsmodell parametriert wird, welches die unvermeidbare Abweichung zwischen dem Nominalmodell und dem tatsächlichen Zellverhalten quantifiziert. Für diese Modellbeschreibung wird ein neuer Algorithmus zur Ladezustandsdiagnose entwickelt, der anstelle eines einzelnen (fehlerbehafteten) Wertes für den Ladezustand ein Vertrauensintervall angibt sowie Artefakte im zeitlichen Verlauf des geschätzten Ladezustandes vermeidet. Die Eigenschaften der Ladezustandsschätzung werden an einer Lithium-Ionen-Zelle und einem Einsatzszenario aus dem automobilen Bereich demonstriert. / In this paper, a new approach to modeling lithium ion cells is presented. In addition to a model that describes the nominal behavior of the cell, an uncertainty model is parameterized which quantifies the unavoidable difference between the nominal model and the true system behavior. For this model description a new algorithm for state of charge estimation is developed, which provides a confidence interval instead of a single unreliable value for the state of charge and avoids artifacts in the progression of the estimated state of charge over time. The properties of the state of charge estimation are demonstrated on a lithium-ion cell in an automotive application scenario.

In the early 1970s, research carried out on rechargeable lithium batteries at the Exxon Laboratories in the US established that lithium ions can be intercalated electrochemically into certain layered transition-metal sulphides, the most promising being titanium disulphide. Stemming from this discovery for titanium disulphide, there has been increased interest on lithium-ion intercalation compounds for application in rechargeable batteries. The first rechargeable lithium cell was commercialized in late 1980s by Moli Energy Corporation in Canada. The cell comprised a spirally wound lithium foil as the anode, a separator and MoS2 as the cathode. The cell had a nominal voltage of 1.8 V and an attractive value of specific energy, which was 2 to 3 times greater than either lead-acid or nickel-cadmium cells. However, the battery was withdrawn from the market after safety problems were experienced. This paved way for the discovery of lithium-ion battery. The origin of lithium-ion battery lies in the discovery that Li+-ions can be reversibly intercalated within or deintercalated from the van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. Thus, lithium metal is replaced by carbon as the anode material for rechargeable lithium-ion batteries, and the problems associated with metallic lithium mitigated. Complimentary investigations on intercalation compounds based on transition metals resulted in establishing LiCoO2 and LiNiO2 as promising cathode materials. By employing aforesaid intercalation materials, namely carbon and LiCoO2 respectively, as negative and positive electrodes in a non-aqueous lithium-salt electrolyte, a Li-ion cell with a voltage value of about 3.5 V resulted. These findings led to a novel rechargeable battery technology. Lithium-ion batteries were first introduced commercially in 1991 by the Sony Corporation in Japan. Other Japanese manufacturers soon entered the market, followed closely by American and European companies. The subsequent growth in sales of the batteries was truly phenomenal. Beginning from 1991, the lithium-ion battery market has grown from an R&D interest to sales of over 400 million units in 1999. The global market value for lithium-ion batteries at original equipment manufacturer level was estimated to be $1.86 billion in 2000. By 2006, the market is expected to grow to over 1.2 billion units with value of over $4 billion, while the average unit price is expected to fall. Initially, realizable specific energy of commercial Li-ion battery was only about 120 Wh kg-1. However, with continuing improvements in various cell components, present day Li-ion batteries can provide a specific energy density of about 200 Wh kg-1. With the ‘holy grail’ far to be realized, the current R&D efforts are focussed on furthering the specific energy of lithium-ion batteries in conjunction with safety, environmental compatibility, and cost effectiveness. In the Li-ion cell, all of its electrochemical constituents, namely anode, cathode and electrolyte are central to its performance. This thesis describes some novel studies on cathode and anode materials for lithium-ion Batteries.

Les batteries lithium-ion sont considérées de nos jours comme la solution optimale pour les systèmes de stockage d'énergie, et cela est dû principalement à leurs hautes densités d'énergie et de puissance. Leurs performances, durées de vie, et fiabilités sont liées et dépendent des conditions d'utilisations telles que la température et les courants demandés par l'application. Et afin d'avoir un suivi de l'évolution du vieillissement de la batterie, la détermination de son état de santé (State-Of-Health -SOH-) est une fonction majeure à considérer. Ce mémoire expose les méthodologies ou techniques développées pour la gestion de la durée de vie de la batterie lithium-ion, et plus particulièrement pour la détermination de son état de santé, en se basant sur ses propres paramètres principaux qui sont la capacité et la résistance ohmique. Cette démarche permet de basculer d'un SOH statique (basé sur un modèle prédéfini de vieillissement tenant compte du calendaire et du cyclage en fonction des caractéristiques telles que la température et le courant de la batterie suivies en temps réel) vers un SOH dynamique ou auto-adaptatif, puisqu'il est basé sur un modèle du composant électrochimique dont les paramètres précédents sont évaluées en temps réel en fonction des conditions d?utilisation. Le premier chapitre revient sur les généralités concernant la technologie lithium-ion : caractéristiques, performances, constitution de l'élément de stockage, choix et nature des électrodes... Le principe de fonctionnement avec les équations générales des phénomènes électrochimiques sont aussi développés. Le second chapitre est un état de l'art des méthodologies de prédiction de la durée de vie avec les différentes classifications des modèles et des techniques de prédiction. Puis lors du troisième chapitre, nous aborderons nos méthodologies développées et les techniques utilisées, telles que le calcul statistique, la logique floue et les lois de vieillissement pour la détermination d'un état de santé dynamique de la batterie, qui en plus de la prise en compte de l'état de santé statique, c'est-à-dire basé seulement sur le vieillissement calendaire et en cyclage, considérera aussi l'évolution de la capacité et de la résistance ohmique de la batterie, en fonction du temps et des conditions d'utilisation, permettant ainsi de considérer les phénomènes improbables. Enfin dans le dernier chapitre, nous exposerons les résultats obtenus lors des tests de validations sur banc de puissance et de prototypage rapide sur des éléments réels / Lithium-ion batteries are considered nowadays as the optimal issue for the energy storage systems, it is mainly due to their high energy and power density. Their performances, lifetime, and reliability are related and depend on the operating conditions such as the temperature and requested current by the application. And in order to track the evolution of the ageing of the battery, the determination of its State-Of-Health -SOH- is a major function to consider. This thesis presents both methodologies and techniques developed for the management of the lifetime of lithium-ion battery, and more particularly the assessment of its state-of-health, based on its own main parameters which are the capacity and the ohmic resistance. This approach allows to switch from a static SOH (based on a predefined ageing model, which take into account the calendar and cycling ageing of the battery, according to some characteristics such as the temperature and the courant of the battery tracked in real time) to a dynamic SOH (self-adaptive) using an online assessment of the previous parameters according to the operating conditions. The first chapter is an overview about the lithium-ion technology: characteristics, performances, cell design, choice and nature of the electrodes... The operating principle with the general equations are also developed. The second chapter is a state of the art of the lifetime prediction methodologies with the different kinds of classification of models and prediction techniques. Then in the third chapter, we will discuss our methodologies and the developed techniques, such as the use of statistics, fuzzy logic and rules of ageing to assess a dynamic state of health of the battery, which not only does take into account the static SOH (calendar and cycling ageing), but also considers the evolution of the ohmic resistance and the capacity of the battery, depending on the time and the operating conditions. This allows taking into consideration unlikely phenomena. Finally, in the last chapter, we will expose obtained results from validation tests. These tests were done under a power electrical testbench and a rapid prototyping testbench with real cells

A galvanic cell converts chemical energy into electrical energy. Devices that carry out these conversions are called batteries. In batteries, generally the chemical components are contained within the device itself. If the reactants are supplied from an external source as they are consumed, the device is called a fuel cell. A fuel cell converts chemical energy into electrical energy as long as the chemicals are supplied from external reserves. The working principle of a metal-air battery involves the principles of both batteries and fuel cells. The anode of a metal-air cell is stored inside the cell, whereas O2 for the air-electrode is supplied from either atmosphere or a tank. There are several metal-air batteries available academically, which include Zn-air, Alair, Fe-air, Mg-air, Ca-air, Li-air and Na-air batteries. So far, only Zn-air battery is successfully commercialized. Li-air battery is attractive compared to other metal-air batteries because of its high theoretical energy density (11140 Wh kg-1). The energy density of Li-air battery is 3 - 5 times greater than state-of-art Li-ion battery. Li-air (or Li-O2) battery comprises Li-metal as the anode and a porous cathode. The cathode and the anode are separated by a suitable separator soaked in an organic electrolyte. Atmospheric air can enter the battery through the porous cathode. Out of the mixture of gases present in the air, only O2 is electrochemically active. For optimization purpose, most of researchers use pure O2 gas instead of air. Li-air battery is not commercialized till now because of several issues associated with it. The issues include: (i) sluggish kinetics of O2 electrode reaction, (ii) decomposition of the electrolyte during charge-discharge cycling, (iii) formation of Li dendrites, (iv) contamination by moisture, etc. Among these scientific and technical problems related to Li-O2 cell system, studies on rechargeable O2 electrode with fast kinetics of oxygen reduction reaction (ORR) during the cell discharge and oxygen evolution reaction (OER) during charge in non-aqueous electrolytes are important. In non-aqueous electrolytes, the 1-electron reduction of O2 to form superoxide (O2 -) is known to occur as the first step. (ii) Subsequently, superoxide undergoes reduction to peroxide (O2 2-) and then to oxide (O2-). The kinetics of ORR is slow in non-aqueous electrolytes. Furthermore, the reaction needs to be reversible for rechargeable Li-air batteries. In order to realize fast kinetics, a suitable catalyst is essential. The catalyst should be bifunctional for both of ORR and OER in rechargeable battery applications. Noble metal particles have been rarely investigated as catalysts for O2 electrode of Li-O2 cells. Graphene has two-dimensional planar structure with sp2 bonded carbon atoms. It has become an important electrode material owing to its high electronic conductivity and large surface area. It has been investigated for applications such as supercapacitors, Li-ion batteries, and fuel cells. Catalyst nanoparticles prepared and anchored to graphene sheets are expected to sustain discrete existence without undergoing agglomeration and therefore they possess a high catalytic stability for long term experiments as well as applications. In this context, it is intended to explore the catalytic activity of noble metal nanoparticles dispersed on reduced graphene oxide (RGO) for O2 electrode of Li-O2 cells. While a majority of the investigations reported in the thesis involves noble metal and alloy particles dispersed on RGO sheets, results on polypyrrole-RGO composite and also magnesium cobalt silicate for Li-O2 system are included. A chapter on electrochemical impedance analysis of LiMn2O4, a cathode material of Li-ion batteries, is also presented in the thesis. Introduction on electrochemical energy storage systems, in particular on Li-O2 system is provided in the 1st Chapter of the thesis. Synthesis of Ag nanoparticles anchored to RGO and catalytic activity are presented in the 2nd Chapter. Ag-RGO is prepared by insitu reduction of Ag+ ions and graphene oxide in aqueous phase by ethylene glycol as the reducing agent. The product is characterized by powder XRD, UV-VIS, IR, Raman, AFM, XPS, SEM and TEM studies. The SEM images show the layered morphology of graphene and TEM images confirm the presence of Ag nanoparticles of average diameter less than 5 nm anchored to RGO (Fig. 1a). Ag-RGO is investigated for ORR in alkaline (1 M KOH), neutral (1 M K2SO4) and non-aqueous 0.1 M tetrabutyl ammonium perchlorate in dimethyl sulphoxide (TBAP-DMSO) electrolytes. The ORR follows 4e- reduction in aqueous and 1e- reduction pathway in non-aqueous electrolytes. Li-O2 cells are assembled with Ag-RGO as (iii) Fig. 1. (a) TEM image of Ag-RGO and (b) charge-discharge voltage profiles of Li-O2 (Ag-RGO) cells. oxygen electrode catalyst in non-aqueous electrolyte (1 M LiPF6-DMSO) and subjected to charge-discharge cycling at several current densities. The discharge capacity values obtained are 11950 (11.29), 9340 (5.00), and 2780 mAh g-1 (2.47 mAh cm-2) when discharged at 0.2, 0.5, 0.8 mA cm-2, respectively (Fig. 1b). Powder XRD studies of discharged electrodes indicate the formation of Li2O2 and Li2O during the cell discharge. In addition to these studies, Na-O2 cells are also assembled with Ag-RGO in non-aqueous electrolyte. It is concluded that the chemistry Li-O2 and Na-O2 cells are similar except for the capacity values. Metal nanoparticles of Au, Pd and Ir are decorated on RGO sheets by reduction of metal ions on graphene oxide by NaBH4. Au-RGO, Pd-RGO and Ir-RGO are characterized by various physicochemical techniques. Particle size of metal nanoparticles ranges from 2 to Fig.2. Charge-discharge voltage profiles Li-O2(RGO) (i) and Li-O2(Au-RGO) (ii) cells at current density 0.3 mA cm-2. 0 2500 5000 7500 10000 12500 15000 10 nm on graphene sheets. All samples are studied for ORR in aqueous and non-aqueous electrolytes by cyclic voltammetry and rotating disk electrode experiments. Li-O2 cells are assembled in 1 M LiPF6-DMSO and discharge capacity values obtained are 3344, 8192 and 11449 mAh g-1 with Au-RGO, Pd-RGO and Ir-RGO, respectively, at 0.2 mA cm-2 current density. The results of these studies are described in Chapter 3. Synthesis and electrochemical activity of Pt-based alloy nanoparticles (Pt3Ni, Pt3Co and Pt3Fe) on RGO are presented in Chapter 4. The Pt3Ni alloy particles are prepared by simultaneous reduction of Pt4+, Ni2+ and graphene oxide by hydrazine in ethylene glycol medium. Pt3Co-RGO and Pt3Fe-RGO are also prepared similar to Pt3Ni-RGO. Formation of alloys is confirmed with XRD studies. O2 reduction reaction on Pt-alloys in non-aqueous electrolyte follows 1e- reduction to O2 -. RDE results show that Pt3Ni-RGO is a better catalyst than Pt for O2 reduction (Fig. 3). Li-O2 cells are assembled with all samples and subjected to Fig. 3. Linear sweep voltammograms of Pt3Ni-RGO, Pt3Co-RGO and Pt3Fe-RGO in 0.1 M TBAPDMSO with 1600 rpm at 10 mV s-1 scan rate. The area of GC electrode was 0.0314 cm2 with a catalyst mass of 200 μg. charge-discharge cycling at several current densities. The initial discharge capacity values obtained are 14128, 5000 and 10500 mAh g-1 with Pt3Ni-RGO, Pt3Co-RGO and Pt3Fe-RGO, respectively, as the air electrode catalysts. Polypyrrole (PPY) is an attractive conducting polymer with advantages such as high electronic conductivity and electrochemical stability. A combination of advantages of graphene and PPY composite are explained in the Chapter 5. PPY is grown on already synthesized RGO sheets by oxidative polymerization of pyrrole in an acidic PY composite is characterized by XRD and Raman spectroscopy studies. Li-O2 cells are assembled in non-aqueous electrolyte and subjected for charge-discharge cycling at different current densities. The discharge capacity value of Li-O2(PPY-RGO) cell is 3358 mAh g-1 Fig. 4. (a) Discharge-charge performance of Li-O2(PPY-RGO) cell with a current density of 0.2 mA cm-2 limiting to a capacity of 1000 mAh g-1 and (b) variation of cut-off voltages on cycling. (3.94 mAh cm-2) in the first cycle. Li-O2(PPY-RGO) cell delivers 3.7 times greater discharge capacity than Li-O2(RGO) cell. Cycling stability of Li-O2 (PPY-RGO) cell is investigated by charge-discharge cycling by limiting the capacity to 1000 mAh g-1, and the cell voltage at the end of discharge and at the end of charge are found constant at 2.75 and 4.10 V, respectively (Fig. 4 a, b). This study shows that PPY-RGO is stable in Li-O2 cells. Electrochemical impedance study shows that charge-transfer resistant is 500 Ω for freshly assembled Li- O2(PPY-RGO) cell and it decreases to 200 Ω after 1st discharge. Synthesis of magnesium cobalt silicate and its electrochemical activity are presented in Chapter 6. MgCoSiO4 is synthesized by mixed solvothermal approach and characterized by various physicochemical techniques. Cubic shaped MgCoSiO4 is investigated for oxygen evolution reaction (OER) activity in alkaline and neutral media. The current values at 0.95 versus SHE are 43, 0.18, 16 mA cm-2 on MgCoSiO4, bare carbon paper and Pt foil electrodes, respectively (Fig. 5), indicating that MgCoSiO4 is a good catalyst for OER. The onset potential for OER is 0.68 V versus SHE on MgCoSiO4 in 1 M KOH. OER activity on MgCoSiO4 is also studied in K2SO4 and phosphate buffer electrolytes. The results indicate good catalytic activity of MgCoSiO4 in neutral electrolytes also. The catalytic activity of Fig. 5. Cyclic voltammograms of bare carbon paper (i), Pt foil (ii), MgCoSiO4 coated carbon (iii) electrodes in 1 M KOH (sweep rate = 5 mV s-1, loading level = 1.15 mg, area = 0.5 cm-2). MgCoSiO4 towards ORR in aqueous and non-aqueous electrolytes is studied by RDE experiments. Li-O2 cells are assembled with bifunctional MgCoSiO4 catalyst in 1 M LiPF6- DMSO electrolyte and the discharge capacity values obtained are 7721 (8.27), 2510 (1.66) and 1053 mAh g-1 (0.92 mAh cm-2) when discharged at 0.3, 0.5 and 0.8 mA cm-2 current densities, respectively. Electrochemical impedance spectroscopy (EIS) measurements of LiMn2O4 electrode are carried out at different temperatures from -10 to 50 0C and in the potential range from 3.50 to 4.30 V, and the data are analysed in Chapter 7. In the EIS spectra recorded over the frequency range from 100 kHz to 0.01 Hz at different temperatures, there are two semicircles present in the Nyquist plot (Fig. 6a). But in 3.90 to 4.10 V versus Li/Li+(1M) potential range at low temperatures (-10 to 15 oC) range, another semicircle also appears (Fig. 6b). Impedance parameters such as solution resistant (Rs), charge-transfer resistance (Rct), doublelayer capacitance (Cdl), electronic resistance (Re) and Warburg impedance (WR), etc., are obtained by analysis of the EIS data. The variations of resistances with temperature are analysed by Arrhenius-like relationships and the apparent activation energies of the corresponding transport properties are evaluated. The values of activation energy for chargetransfer process are 0.37, 0.30 and 0.42 eV, at 3.50, 3.90 and 4.10 V versus Li/Li+(1M), respectively. The chemical diffusion coefficient of Li+ ions into LiMn2O4 calculated from EIS data. The values of diffusion coefficient calculated are in the range of 2.50 x 10-12 - 4.10 Fig. 6. Nyquist plot of impedance study of Li/LiMn2O4 cell at 3.50 V (a) and 3.90 V (b) at -10 0C. Details of the above studies are described in the thesis.

The aim of this work is to describe the influence of temperature on the structure and chemical composition of electrode materials for Li-ion accumulators. Theoretical part of this thesis contains described terminology and general issues of batteries and their division. Every kind of battery is provided with a closer description of a specific battery type. A separate chapter is dedicated to lithium cells, mainly Li-ion batteries. Considering various composition of Li-ion batteries, the next subchapters deeply analyzes the most used cathode (with an emphasis on the LiFePO4, LiMn1/3Ni1/3Co1/3O2) and anode materials (with an emphasis on the Li4Ti5O12). The next chapters describe the used analytical methods: electron microscopy, energy dispersion spectroscopy and thermomechanical analysis. The practical part is devoted to the description of the individual experiments and the achieved results.