<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>

In the first part of his work, the causes for the sudden degradation of useable capacity of lithium-ion cells have been studied by means of complementary methods such as computed tomography, Post-Mortem studies and electrochemical analyses. The results obtained point unanimously to heterogeneous aging as a key-factor for the sudden degradation of cell capacity, which in turn is triggered by differences in local compression. At high states of health, the capacity fade rate is moderate but some areas of the graphite electrode degrade faster than others. Still, the localized changes are hardly noticeable on cell level due to averaging effects. Lithium plating occurs first in unevenly compressed areas, creating patterns visible to the human eye. As lithium plating leads to rapid consumption of active lithium, a sudden drop in capacity is observed on cell level. Lithium plating appears to spread out from the initial areas over the whole graphite electrode, quickly consuming the remaining useful lithium and active graphite. It can be hypothesized that a self-amplifying circle of reciprocal acceleration of local lithium loss and material loss causes rapid local degradation. Battery cell designers can improve cycle life by homogeneous pressure distribution in the cell and using negative active materials that are resilient to elevated discharge potentials such as improved carbons or lithium titanate. Also, a sufficiently oversized negative electrode and suitable electrolyte additives can help to avoid lithium plating. When packs are designed, care must be taken not to exert local pressure on parts of cells and to avoid both very high and low states of charge. In the second part of this dissertation the resilience of cylindrical and pouchbag cells to shocks and different vibrations was investigated. Stresses inflicted by vibration and shock tests according to the widely recognized UN38.3 transport test were compared to a long-time test that exposed cells to a 186 days long ordeal of sine sweep vibrations with a profile based on real-world applications. All cells passed visual and electric inspection performed by TU München after the vibration tests. Only cylindrical cells subjected to long-term vibrations in axial direction showed an increase in impedance and a loss of capacity that could be recuperated in part. The detailed analyses presented in this thesis gave more details on the damages inflicted by vibrations and shocks and revealed drastic damages in some cases. In cylindrical cells, only movement in axial direction caused damage. Long term vibrations were found to be especially detrimental. No damage whatsoever could be detected for pouch cells, regardless of the test protocol and the direction of movement. The extreme resilience of pouchbag cells shows that the electrode stack of lithium-ion cells is resistant to vibrations, and that damages are caused by design imperfections that can be improved at low cost. The findings of this work, and the general state of research show that it is most crucial to control the lithiation and thus potential of the graphite electrode. In the last part of this work, a new, direct method for charge estimation based on changing transmission is presented. A correlation between transmission of short ultrasonic pulses and state of charge is found. This new technology allows direct measurement of the state of charge. The method is demonstrated for batteries with different positive active materials, showing its versatility. As the observed changes can be traced to the lithiation of graphite, it can be determined without a reference electrode. Already at this early stage of development, the found correlations allow estimation of state of charge. The present hysteresis in the signal height of the slow wave, which is unneglectable especially during discharging at higher currents, will be subject to further investigation. The observed effects can be explained by effects on different length scales. Biot’s theory explains the second wave’s slowness based on the active material particles size in the range of 0.01 mm and electrolyte-filled pores. Lithiation of graphite changes the porosity of the electrode and thereby the velocity and wavelength of the impulse. When the wavelength approaches the length scale of the layers, 0.1 mm, scattering effects dampen the transmitted signal. Finally, the wavelength of the pulse should be shorter than the transducers diameter to obtain a homogeneous wave front. To conclude, the new method allows the control of each individual cell in a pack independent from the electrical connections of the cells. As the method shows great promise, further studies regarding factors such as long-term behavior, temperature and current rates should be conducted. In this thesis hysteresis was observed and a deeper understanding of the reasons behind it may allow further improvements of measurement precision. / Im ersten Teil dieser Doktorarbeit wurden die Ursachen des plötzlichen Kapazitätseinbruchs von Lithium-Ionen Zellen untersucht. Die mittels sich ergänzender Methoden wie Röntgentomographie, Post-Mortem Untersuchungen und elektrochemischer Analysen gewonnenen Ergebnisse weisen darauf hin, dass heterogene Alterungseffekte eine Schlüsselrolle für den beschleunigten Kapazitätsverlust spielen. Die beobachteten Ungleichmäßigkeiten auf gealterten Elektroden konnten wiederum auf Kompressionsunterschiede zurückgeführt werden. Im frühen Alterungsstadium war zwar nur ein moderater Kapazitätsverlust zu verzeichnen, einige Bereiche der Graphitelektrode altern jedoch schneller als andere. Diese lokalen Alterungseffekte sind auf Zellebene aufgrund von Mittelungseffekten zunächst schwer nachweisbar, sobald jedoch in Bereichen abweichender Kompression Lithiumplating auftritt, entstehen Muster welche nach Öffnen der Zelle gut zu erkennen sind. Inaktives Lithium, dicke Passivschichten sowie erhöhte Mengen an abgelagertem Mangan und anderen Metallen die aus dem positiven Aktivmaterial herausgewaschen wurden, konnten in geschädigten Bereichen der Zellen B und C, welche direkt beim Einsetzen beziehungsweise 150 Zyklen später geöffnet wurden, nachgewiesen werden. Da Lithiumplating zu raschem Verbrauch von aktivem Lithium führt, kann ein plötzlicher Einbruch der Zellkapazität beobachtet werden. Das Lithiumplating scheint sich von den geschädigten Bereichen über die gesamte Elektrode auszubreiten, wobei rasch das verbleibende aktive Lithium und teilweise auch das negative Aktivmaterial verbraucht wird. Daher wird die Hypothese aufgestellt, dass durch lokales Lithiumplating ein sich selbst verstärkender Kreislauf in Gang gesetzt wird, wobei sich lokaler Lithium- und Aktivmaterialverlust gegenseitig beschleunigen. Im zweiten Teil der Arbeit wurde die Widerstandsfähigkeit von zylindrischen und Pouchbagzellen gegenüber Schocks und Vibrationen untersucht. Belastungen durch Vibrationen und Schocks gemäß des weitläufig anerkannten Transporttests UN38.3 wurden mit 186 Tage dauernden Langzeittests verglichen. Alle Zellen bestanden die visuellen und elektrischen Überprüfungen die an der TU München nach Durchführung der Vibrationstests durchgeführt wurden. Nur die zylindrischen Zellen zeigten einen Anstieg des Innenwiderstands sowie einen weitgehend reversiblen Kapazitätsverlust. Die in dieser Arbeit vorgestellte tiefergehenden Analysen gaben ein detaillierteres Bild der beobachteten Effekte auf und zeigten teilweise schwere versteckte Schäden auf, wobei ausschließlich in axialer Richtung belastete Rundzellen Schäden aufwiesen. Langzeitvibrationen führten zu besonders schweren Schadensbildern. An den untersuchten Pouchzellen konnte keinerlei Schädigung durch die Vibration festgestellt werden. Die Widerstandsfähigkeit der Pouchzellen zeigt, dass der Elektrodenstapel, der die Grundlage jeder Lithium-Ionen Zelle bildet, äußerst vibrationsstabil ist und auftretende Schäden auf ungenügendes Zelldesign zurückzuführen sind. Die hier vorgestellten Ergebnisse und der Stand der Wissenschaft zeigen die Bedeutung des Lithiierungsgrad der Graphitelektrode für die Alterung auf. Im letzten Teil der Arbeit wurde daher eine neue Methode zur Ladezustandsbestimmung mittels Ultraschall vorgestellt. Die beobachteten Amplituden- und Laufzeitänderungen erlauben die direkte Bestimmung des Ladezustands von Lithium-Ionen Zellen und die Anwendbarkeit konnte an Zellen mit verschiedenen positiven Aktivmaterialien gezeigt werden. Die beobachteten Effekte können auf Vorgänge auf verschiedenen Längenskalen zurückgeführt werden. Biots Theorie bietet eine Erklärung der geringen Geschwindigkeit der zweiten Welle aufgrund der Ausbreitungsmodi der Schallwellen im porösen, elektrolytgefüllten Aktivmaterial. Die im Vergleich zur Wellenlänge kleine Längenskala der Aktivpartikel und der elektrolytgefüllten Poren von 0,01 mm führt hierbei dazu, dass sich das Material als Effektivmedium verhält. Durch die Lithiierung der Graphitpartikel ändern sich Eigenschaften und Porosität der Elektrode. Insbesondere die Porositätsänderung kann laut Biots Theorie die Geschwindigkeit und somit die Wellenlänge der zweiten Welle wesentlich verändern. Wenn die Wellenlänge auf die Größenordnung der Schichtdicken der Zelle, 0,1 mm, reduziert wird, treten Streuungseffekte auf, die die transmittierte Welle abschwächen. Schlussendlich muss der Durchmesser der eingesetzten Schallwandler größer als die Wellenlänge der Pulse sein um ein homogenes Schallfeld zu erzeugen. Da der Einsatz von Ultraschallpulsen vielversprechend erscheint, sollten in weiteren Studien Faktoren wie Langzeitverhalten, Temperatur- und Rateneinflüsse untersucht werden. In dieser Arbeit wurde weiterhin Hysterese beobachtet deren tieferes Verständnis nicht nur die Ladezustandsbestimmung, sondern auch das Verständnis der dynamischen Prozesse in Lithium-Ionen Zellen verbessern könnte.

<p> In the pursuit to enable the rapid charging of lithium-ion batteries, lithium plating at the anode  poses one of the most significant challenges. Additionally, the heat generation that accompanies  high rate battery operation in conjunction with non-uniform cooling and localized heating at tabs  is known to result in thermal inhomogeneity. Such thermal anomalies in the absence of proper  thermal management can instigate accelerated degradation in the cell. This work seeks to elucidate  the link between thermal gradients and lithium plating in lithium-ion batteries using a combined  experimental and simulation-based approach. First, we experimentally characterize the lithium  plating phenomenon on graphite anodes under a wide variety of charging rates and temperatures  to gain mechanistic insights into the processes at play. An in operando detection method for the  onset of dendritic lithium plating is developed. Lithium plating regimes are identified as either  nucleate or dendritic, which exhibit vast differences in reversibility. An operando method to  quantify lithium stripping based on the rest phase voltage plateau is presented. Next, a model is  employed to provide fundamental insights to the thermo-electrochemical interactions during  charging in scenarios involving an externally imposed in-plane and inter-electrode thermal  gradient. The relative importance of in-plane vs. inter-electrode thermal gradients to charging  performance and cell degradation is necessary to inform future cell design and cooling systems for  large-format cells, which are crucial for meeting the energy requirements of applications like  electric vehicles. While in-plane thermal gradients strongly influence active material utilization,  the lithium plating severity was found to be very similar to an isothermal case at the same mean  temperature. By contrast, inter-electrode thermal gradients cause a shifting on the solid phase  potential at each electrode during charging, related to the increase or decrease in overpotential due  to local temperature variation. An experiment is then performed on a commercial multi-layer  pouch cell, in which it was found that applied thermal gradients provide a slight reduction in  lithium plating severity and degradation rate when compared to an isothermal cell at the same  mean temperature. The presence of a thermal gradient causes heterogeneous lithium plating  deposition within the cell, with colder regions experiencing higher quantities of plating and larger  thermal gradients leading to more severe heterogeneity.   </p>

This work develops three models for simulation of the high-current operation of Li-ion batteries. Simulation as a tool can provide understanding beyond what experiments can offer. Different types of electrodes such as graphite, silicon, and NMC are modeled to study cell performance and aging under aggressive operating conditions. The first part of this work focuses on the effect of electrode microscale lateral heterogeneity on the degradation of conventional Li-ion batteries, especially for fast-charge applications. The non-uniform pore distribution leads to the nonuniform current density and state of charge (SoC), which can finally result in non-uniform Li plating and aging. The interactions of electrode regions a few mm away from each other with different ionic conductivity are simulated by combining conventional models in parallel with submodels to treat additional physics. The onset and growth of lithium metal deposits on the anode are predicted. The next topic is to investigate the structure of multilayer anodes (MLA) consisting of two layers in the through-plane direction with different ionic resistances. The model is intended to simulate a commercially made cell. Simulation results demonstrate that coating a higher-density layer near the current collector and a lower-density layer near the separator provides improved accessibility to active material during cell fast charge through better ionic transport. In addition, the improved anode further augments the cathode performance in high-current discharges, leading to greater energy density and power density of the cell. The last topic is to develop a numerically efficient mechanical and electrochemical model for silicon anodes. Silicon has a much higher energy density than graphite as a material for the anode; however, it undergoes high volume expansion and contraction ($\sim$ 280\%) which affects cell thickness and electrode ionic transport. The mechanical model treats these volume-change phenomena in a continuum fashion and is integrated into a P2D model of a Si half cell. As shown by the model, the external casing material of such cells can improve or restrict electrode utilization. Different cell designs are simulated to predict the degree of lithiation.

With an increasing demand for sustainable transport solutions, there is a demand for electrified vehicles. One way to store energy on board an electrified vehicle is to use a lithium-ion battery (LIB). This battery technology has many advantages, such as being rechargeable and enabling reasonably high power output and capacity. To ensure reliable operation of LIB:s, the battery management system (BMS) must be designed with regards to the electrochemical dynamics of the battery. However, since the battery ages over time, the dynamics changes as well. It is possible to predict ageing, but some ageing mechanisms can occur randomly, e.g. due to variations of circumstances during manufacturing, and variations of battery user choices. Hence, by monitoring ageing mechanisms in situ, the BMS can adapt accordingly, similar to a closed loop control system. One ageing mechanism in LIB:s is lithium plating. This mechanism signifies when Li ions are electrochemically deposited as metal onto the negative electrode of the LIB during charging, and can induce other ageing mechanisms, such as gassing or electrolyte reduction. The present project has investigated a method for detecting Li plating in situ after its occurrence by both analysing the voltage change over time during open-circuit voltage (OCV) periods after charging and monitoring battery swelling forces. Results show a correlation between a high probability of Li plating and the appearance of a swelling force peak and an OCV plateau. However, results also show a possible correlation between the onset of Li plating and the onset of the swelling force peak, while also showing a greater detectability of the force signal compared to the electrochemical signal. Furthermore, the present results show that the magnitudes of both signals are probably related to the amount of plated Li. The amount of irreversibly lost Li from plating is shown to have a possible correlation with accumulation of swelling pressure. However, to further validate the feasibility of these two signals, more advanced analysis is required, which was not available during this project. / Med en ökande efterfråga på hållbara transportlösningar så finns det ett behov av elektrifierade fordon. Ett sätt att lagra energi ombord ett elektrifierat fordon är att använda et litium-jon-batteri. Denna batteriteknologi har många fördelar: t.ex. är dessa batterier återladdningsbara, och de kan leverera höga uteffekter samtidigt som de kan ha ett stort energiinnehåll. för att säkerställa en säker drift av litium-jon-batterier måste batteriets styrsystem vara designat med hänsyn till den elektrokemiska dynamiken inuti batteriet. Dock åldras batteriet med tiden, vilket innebär att denna dynamik ändras med tiden, vilket innebär att styrningen av batteriet måste anpassa sig till denna föråldring. Det är möjligt att förutspå åldring av batterier, men vissa åldringsmekanismer kan ske slumpartat, t.ex. via slumpmässiga förändringar i tillverkningsprocessen av batteriet, eller variationer i användningen av batteriet. Genom att därmed bevaka dessa åldringsmekanismer in situ så kan styrsystemets algoritm anpassa sig utmed batteriåldringen, trots dessa slumpartade effekter. En åldringmekanism hos litium-jon-batterier är s.k. litiumplätering. Denna mekanism innebär att litium-joner elektrokemiskt pläteras i form av metalliskt litium på ytan av litium-jon-batteriets negativa elektrod. Mekanismen kan också inducera andra åldringsmekanismer, t.ex. gasutveckling eller elektrolytreduktion. Detta projekt har undersökt en metod för att detektera litiumplätering in situ efter att plätering har skett, genom att både analysera öppencellspänningens (OCV) förändring med tiden direkt efter uppladdning samt analysera de svällande krafterna som uppstår under uppladdning av batteriet. Resultaten visar på en korrelation mellan en hög sannolikhet för litiumplätering och observationen av en topp i svällningskraft och en platå i OCV-kurvan. resultaten visar också en möjlig korrelation mellan påbörjandet av litium-plätering och påbörjandet av toppen i svällningskraft. Vidare visar även resultaten ett troligt samband mellan signalernas magnitud och mängden pläterat litium. Slutligen visar resultaten också ett möjligt samband mellan irreversibelt pläterat litium och ett svällningstryck som ackumuleras med varje uppladdningscykel. Dock krävs det en validering med mer avancerade analysmetoder för att säkerställa användningsbarheten av dessa två signaler, vilket ej var möjligt inom detta projekt.

Lithium ion batteries (LIBs) are widely used for storing and converting chemical energy into electrical energy. During battery operation, lithium ions move between electrode materials, enabling energy storage. However, aging mechanisms like lithium plating can negatively impact battery performance and lifetime. Lithium plating occurs when lithium ions are reduced to metallic lithium on the graphite electrode. The undesired Li plating in LIBs leads to dendrite formation that may puncture the separator, causing internal short-circuit and ultimately thermal runaway. This study aims to investigate the internal processes of LIBs during charge and discharge. Two analysis methods are employed: online electrochemical mass spectrometry (OEMS) and acoustic emission monitoring (AEM). OEMS is a gas analysis technique that combines electrochemical measurements with mass spectrometry to provide real-time testing of cells. OEMS allows identifying and quantifying gas evolution/consumption of chemical species. AE is a diagnostic tool, offering monitoring the health of LIBs through detection and characterisation of stress waves produced by parasitic mechano-electrochemical events. The results indicates that the formation of SEI thin film layer, generated gases like hydrogen and ethylene, while consuming carbon dioxide. During induced lithium plating, hydrogen and carbon dioxide were consumed, and ethylene gas was produced, due to new SEI film formation process. The acoustic emission analysis indicated that lithium plating was an active process, whereas SEI formation was less AE active. Further research is needed to understand the relationships and significance of these processes for battery performance and safety. Overall, this study highlighted the importance of investigating aging mechanisms in LIBs to enhance their performance and longevity. By combining OEMS and AE, it was possible to analyse the batteries behaviour during cycling. The evolution of gas and acoustic signals provided insights into the reactions and processes occurring inside the battery during cycling.

<p>Fast charging is crucial to the proliferation of electric vehicles. Fast charging is limited by lithium plating, which is the deposition of lithium metal on the anode surface instead of intercalation of lithium into the anode. Lithium plating causes capacity fade, increases cell resistance, and presents safety issues. A fast charging strategy was implemented using a battery management system (BMS) that avoided lithium plating by predicting the anode impedance. Commercial pouch cells modified with a reference electrode were cycled with and without the BMS. Cells cycled with the BMS avoided lithium plating but experienced significant degradation at the cathode. Cells cycled without the BMS underwent extensive lithium plating at the anode. Capacity loss was differentiated into irreversible and irretrievable capacity to understand electrode-based degradation mechanisms. Post-mortem analysis on harvested electrodes showed that the BMS cycled cells exhibited minimal anode degradation and had a two-times higher capacity loss on the cathode. The cells cycled without the BMS had extensive anode degradation caused by lithium plating and a seven-times higher capacity loss on the anode. </p> <p> </p> <p>Understanding and preventing the aging mechanisms of lithium-ion batteries is necessary to prolong battery life. Traditional full cell measurements are limited because they cannot differentiate between degradation processes that occur separately on anode and cathode. A reference electrode was inserted into commercial cylindrical lithium-ion cells to deconvolute the anode and cathode performance from the overall cell performance. Two configurations of the reference electrode placement inside the cell were tested to find a location that was stable and had minimal interference on the full cell performance. The reference electrode inside the mandrel of the cylindrical cell had stable potential measurements for 80 cycles and at different C-rates and had minimal impact on the full cell performance.<b></b></p>

No description available.

<p dir="ltr">Li-ion batteries are ubiquitous in today’s world with portable electronics, EVs making inroads into daily lives, and electric aircraft at the cusp of becoming reality. These and many more applications revolutionize the world with improvements in batteries at scales from materials, manufacturing, electrode architectures, cell design, and protocols. The various challenges associated with the current generation of batteries include the fast-charging capabilities, economic return of the longevity of the battery, and thermal safety characteristics. The aging and degradation of LIBs appears to be a key pain point particularly when exposed to harsh operating temperature and fast charging conditions. LIBs undergo aging due to numerous chemical and physical degradation processes throughout their lifetime owing to their operation. These challenges are exacerbated by the presence of stringent operating conditions including extreme fast charging, and sub-zero temperature resulting in severe degradation and short cycle life. The LIBs also face challenges in their thermal stability characteristics, failing catastrophically when exposed to high temperature or mechanical abuse conditions. The onset and intensity of these thermal runaway behaviors are further modified when batteries undergo varied aging leading to increased heat and gas generation potentially causing fire or explosions. Overall, a comprehensive characterization to delineate the interconnected role and implications of operating extremes and electrode design on electrochemical performance, cell aging, and thermal runaway behavior is critical for better batteries. </p><p dir="ltr">To this end, the role of electrode microstructure in mitigating lithium plating behavior under various operating conditions, including extreme fast charging has been examined. Further, these multi-length scale characteristics of the electrode microstructure are explored via data-driven approaches to study the complex interaction of transport and kinetic limitations on the microstructure designs. A third study is undertaken for in-operando characterization of the LIB degradation, probing the multi-length scale degradation using pulse voltammetry. Here an accurate degradation descriptors dataset is identified and accurately parametrized, throughout its cycling lifespan. These aging behaviors are translated to physio-chemical degradation mechanisms via a reduced-order coupled electrochemical-thermal-aging interactions model. Lastly, the implication of aging behavior on thermal-safety interactions is delineated. Overall the dissertation is focused on developing a fundamental understanding of the LIB performance, degradation, and safety interactions.</p>