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<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>

The wide applications of energy storage systems in consumer electronics, electric vehicles, and grid storage in the recent decade has created an enormous market globally. The electrochemical flow system has many applications in Li-ion battery recycling and energy storage system design. First, research work on a scalable electrochemical flow system is presented to effectively restore the lithium concentration in end-of-life Li-ion cathode materials. An effective recycling process for end-of-life lithium-ion batteries could relieve the environmental burden and retrieve valuable cathode battery materials. The design is validated in a static configuration with both cathode loose powder and cathode electrode sheet. Materials with comparable electrochemical performance to virgin cathode materials are produced after post heat treatment. Second, research contributions in sulfur-based flow battery systems for long-duration energy storage are presented. Sulfur-based redox flow batteries are promising due to their high theoretical capacity, low cost, and high abundance. The speciation of aqueous sulfur solutions with different nominal concentrations, sulfur concentrations, and pH are studied by Raman spectroscopy. Next, a promising aqueous manganese catholyte to couple with the sulfur anolyte for a full flow battery is investigated. Test protocols and quantification metrics for the catholyte are developed. The stability of the catholyte, including self-discharge rate and precipitation rate, is measured via ex-situ characterizations. The electrochemical performance of the catholyte is investigated and optimized via in-situ experiments. The reaction pathway for the precipitation of catholyte is discussed and several mitigation strategies are proposed. Finally, a semi-solid sodium-sulfur flow battery is developed. The electrochemical performance of the sodium-sulfur battery is studied first in a static configuration at an intermediate temperature (150°C). Then a Na-S semi-solid flow cell is assembled and cycled under the two-aliquots and three-aliquots intermittent flow. / Doctor of Philosophy / The market of energy storage systems has been expanding dramatically in recent years due to their wide applications in portable electronics, electric vehicles, and large-scale grid storage. First, the research on the development of an electrochemical flow system in the Li-ion batteries (LIB) recycling process is presented. The improper disposal of end-of-life LIBs will generate flammable hazardous waste. Recycling spent LIBs could ease the environmental burden and replenish valuable resources such as lithium, cobalt, and nickel, and reduce the cost of battery manufacturing. In this study, an electrochemical flow system is designed to restore the end-of-life cathode materials in LIBs. The design has the potential to scale up and is validated with a static configuration. The recycled materials show comparable electrochemical performance to virgin battery cathode materials. Life cycle analysis shows that the recycling process consumes less energy and is more environmentally friendly. Second, the research contribution in sulfur-based flow battery systems for long-duration energy storage is presented. The aqueous sulfur solutions with different nominal concentrations, sulfur concentrations, and pH are studied by Raman spectroscopy. Next, a promising aqueous manganese catholyte to couple with the sulfur anolyte for a full redox flow battery is investigated. The chemical stability of the catholyte, including self-discharge rate and precipitation rate, is measured via ex-situ characterizations. The electrochemical performance of the catholyte is studied and optimized via in-situ experiments. The reaction mechanisms for the precipitation of aqueous manganese solutions are discussed. Finally, a semi-solid sodium-sulfur (Na-S) flow battery is developed. The electrochemical performance of the sodium-sulfur battery is studied first in a static cell at intermediate temperature. Then a Na-S semi-solid flow cell is demonstrated and cycled under the two-aliquots and three-aliquots intermittent flow.

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abstract: Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013

M.Tech (Department of Electronic Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Due to the fickle nature of weather upon which renewable energy sources mostly depend, a shift towards a sustainable renewable energy system should be accompanied with a good intermediate energy storage system, such as a battery bank, set up to store the excess supply from renewable sources during their peak periods. The stored energy can later be utilised to supply a regulated and steady power supply for use during the off-peak periods of these renewable energy sources. Battery banks, however, are often faced with the challenge of charge imbalance due to the disparities that occur in the operating characteristics of the batteries that constitute a bank. When a battery bank with charge imbalance is repeatedly used in applications without an effective battery management system (BMS) through active charge equalisation, there could be an early degradation, loss of efficiency and reduction of service life of the entire batteries in the bank. In this research, a universal battery management system (BMS) in stand-alone photovoltaic application was proposed and designed. The BMS consists majorly of a switched capacitor (SC) active charge equaliser, designed with a unique configuration of high capacitance and relatively low switching frequency, which can be applicable to common battery types used in stand-alone photovoltaic application. The circuit was mathematically optimised to minimise losses attributed to impulsive charging and tested with lead acid, silver calcium, lead calcium and lithium ion batteries being commonly used in stand-alone photovoltaic application. The SC design was verified by comparing its simulation results to the digital oscilloscope results, and with both results showing similar values and graphs, the design configuration was validated. The design introduced a simple control strategy and less complicated circuit configuration process, which can allow an easy setup for local usage. The benefit of its multiple usage with different stand-alone photovoltaic battery types saves the cost of purchasing a different charger and balancer for different battery types. More so, the design is solar energy dependent. This could provide an additional benefit for usage in areas where energy dependence is off-grid.

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Li-ion batteries have gained great popularity among researchers and practitioners as an environmentally friendly energy storage solution for more environmentally friendly electric vehicles (EVs). However, because of the increased demand for Li-ion battery-powered EVs, and some issues with battery design, legislation, collection and sorting, recycling, and material recovery, achieving sustainable mobility through the circularity of Li-ion batteries is a major challenge. This study aims to identify the challenges as well as develop strategies for enhancing the circularity of Li-ion batteries in Sweden. Following a systematic literature review, two primary research questions were investigated: 1) what are the current challenges and opportunities for the circular economy in lithium-ion battery end-of-life management? 2) how the circularity of LIBs in Sweden could be enhanced? This study employed PEST and SWOT analysis, as well as 11 interviews with industry experts and researchers are performed, to determine the strengths, weaknesses, opportunities, and threats in the circularity of lithium-ion batteries in Sweden. Following that, various strategies were developed to address the identified challenges and improve the circular economy of these batteries. Finally, the developed strategies are validated through expert interviews, and various recommendations are outlined. The study's findings are significant and can assist policymakers, investors, and industry professionals concerned with the circularity of lithium-ion batteries in developing appropriate decisions and better planning for the Swedish transportation sector.

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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.