Lithium-ion batteries(LIBs) have dominated the energy storage market in the past two decades. The high specific energy, low self-discharge, relatively high power and low maintenance of LIBs enabled the revolution of electronic devices and electric vehicle industry, changed the communication and transportation styles of the modern world. Although the specific energy of LIBs has increased significantly since first commercialized in 1991, it has reached a bottleneck with current electrode materials. To meet the increasing market demand, it is necessary to develop high capacity electrode materials.<div><br></div><div>Current commercial anode material for LIB is graphite which has a specific capacity of 372 mAh g-1. Other group IV elements (silicon (Si), germanium (Ge), tin (Sn)) have much higher capacities. However, group IV elements have large volume change during lithiation/delithiation, leading to pulverization of active materials and disconnection between electrode particles and current collector, resulting in fast capacity fading. To address this issue, it is essential to understand the microstructural evolution of Si, Ge and Sn during cycling.<br></div><div><br></div><div>This dissertation is mainly focused on the morphological and structural evolution of Sn and Ge based materials. In this dissertation, anin situ focused ion beam-scanning electron microscopy (FIB-SEM) method is developed to investigate the microstructuralevolution of a single electrode particle and correlate with its electrochemical performance. This method is applied toall projects. The first project is to investigate the microstructural evolution of a Sn particle during cycling. Surface structures of Sn particles are monitored and correlated with different states of charge. The second project is to investigate the morphological evolution of Ge particles at different conditions. Different structures (nanopores, cracks, intact surface) appear at different cycling rates. The third project is to study selenium doped Ge (GeSe) anodes. GeSe and Ge particles are tested at the same condition. Se doping forms Li-Ge-Se network, provides fast Li transport and buffers volume change. The fourth project is to study the reaction front of Ge particle during lithiation. Micron-sized Ge particles have two reaction fronts and a wedge shape reaction interface, which is different from the well-known core-shell mode. The fifth project is to investigate antimony (Sb)-coated porous Ge particles. The Sb coating suppresses electrolyte decomposition and porous structure alleviates volume change. The results in this dissertation reveal fundamental information about the reaction mechanism of Sn and Ge anode. The results also show the effects of doping, porous structuring and surface coating of anode materials.</div>

Indiana University-Purdue University Indianapolis (IUPUI) / In the last years, lithium-ion batteries (LIBs) have become the most important energy storage system for consumer electronics, electric vehicles, and smart grids. The development of lithium-ion batteries (LIBs) based on current practice allows an energy density increase estimated at 10% per year. However, the required power for portable electronic devices is predicted to increase at a much faster rate, namely 20% per year. Similarly, the global electric vehicle battery capacity is expected to increase from around 170 GWh per year today to 1.5 TWh per year in 2030--this is an increase of 125% per year. Without a breakthrough in battery design technology, it will be difficult to keep up with the increasing energy demand. To that end, a design methodology to accelerate the LIB development is needed. This can be achieved through the integration of electro-chemical numerical simulations and machine learning algorithms. To help this cause, this study develops a design methodology and framework using Simcenter Battery Design Studio® (BDS) and Bayesian optimization for design and optimization of cylindrical cell type 18650. The materials of the cathode are Nickel-Cobalt-Aluminum (NCA)/Nickel-Manganese-Cobalt-Aluminum (NMCA), anode is graphite, and electrolyte is Lithium hexafluorophosphate (LiPF6). Bayesian optimization has emerged as a powerful gradient-free optimization methodology to solve optimization problems that involve the evaluation of expensive black-box functions. The black-box functions are simulations of the cyclic performance test in Simcenter Battery Design Studio. The physics model used for this study is based on full system model described by Fuller and Newman. It uses Butler-Volmer Equation for ion-transportation across an interface and solvent diffusion model (Ploehn Model) for Aging of Lithium-Ion Battery Cells. The BDS model considers effects of SEI, cell electrode and microstructure dimensions, and charge-discharge rates to simulate battery degradation. Two objectives are optimized: maximization of the specific energy and minimization of the capacity fade. We perform global sensitivity analysis and see that thickness and porosity of the coating of the LIB electrodes that affect the objective functions the most. As such the design variables selected for this study are thickness and porosity of the electrodes. The thickness is restricted to vary from 22microns to 240microns and the porosity varies from 0.22 to 0.54. Two case studies are carried out using the above-mentioned objective functions and parameters. In the first study, cycling tests of 18650 NCA cathode Li-ion cells are simulated. The cells are charged and discharged using a constant 0.2C rate for 500 cycles. In the second case study a cathode active material more relevant to the electric vehicle industry, Nickel-Manganese-Cobalt-Aluminum (NMCA), is used. Here, the cells are cycled for 5 different charge-discharge scenarios to replicate charge-discharge scenario that an EVs battery module experiences. The results show that the design and optimization methodology can identify cells to satisfy the design objective that extend and improve the pareto front outside the original sampling plan for several practical charge-discharge scenarios which maximize energy density and minimize capacity fade.

This thesis aims at formulating and validating models for electrochemical energy storage devices. More specifically, the devices under consideration are lithium ion batteries and polymer electrolyte fuel cells. A model is formulated to describe an experimental cell setup consisting of a LixNi0.8Co0.15Al0.05O2 composite porous electrode with three porous separators and a reference electrode between a current collector and a pure Li planar electrode. The purpose of the study being the identification of possible degradation mechanisms in the cell, the model contains contact resistances between the electronic conductor and the intercalation particles of the porous electrode and between the current collector and the porous electrode. On the basis of this model formulation, an analytical solution is derived for the impedances between each pair of electrodes in the cell. The impedance formulation is used to analyse experimental data obtained for fresh and aged LixNi0.8Co0.15Al0.05O2 composite porous electrodes. Ageing scenarios are formulated based on experimental observations and related published electrochemical and material characterisation studies. A hybrid genetic optimisation technique is used to simultaneously fit the model to the impedance spectra of the fresh, and subsequently also to the aged, electrode at three states of charge. The parameter fitting results in good representations of the experimental impedance spectra by the fitted ones, with the fitted parameter values comparing well to literature values and supporting the assumed ageing scenario. Furthermore, a steady state model for a polymer electrolyte fuel cell is studied under idealised conditions. The cell is assumed to be fed with reactant gases at sufficiently high stoichiometric rates to ensure uniform conditions everywhere in the flow fields such that only the physical phenomena in the porous backings, the porous electrodes and the polymer electrolyte membrane need to be considered. Emphasis is put on how spatially resolved porous electrodes and nonequilibrium water transport across the interface between the gas phase and the ionic conductor affect the model results for the performance of the cell. The future use of the model in higher dimensions and necessary steps towards its validation are briefly discussed.

<p>  </p> <p>Fossil fuel has dominated the global energy market for centuries, and the world is undergoing a great energy revolution from fossil fuel energy to renewable energies, given the concerns on global warming and extreme weather caused by the emission of carbon dioxide. Lithium ion batteries (LIBs) play an irreplaceable role in this incredible energy transition from fossil energy to renewable energy, given their importance in energy storage for electricity grids and promoting the mass adoption of battery electric vehicles (BEVs). Extreme fast charging (XFC) of LIBs, aiming to shorten the charging time to 15 minutes, will significantly improve their adoption in both the EV market and grid energy storage. However, XFC has been significantly hindered by the relatively sluggish Li+ transport within LIBs.</p> <p>Herein, effects caused by increasing charging rates (from 1C, 4C to 6C) on LiNi0.6Mn0.2Co0.2O2 (NMC622) || graphite cell were systematically probed via various characterization methods. From electrochemical test on their rate/long term cycling performance, the significant decrease in available capacity under high charging rates was verified. Structural evolutions of cycled NMC622 cathode and graphite anode were further probed via ex-situ powder diffraction, and it was found that lattice parameters <em>a</em> and <em>c</em> of NMC622 experience irreversible evolution due to loss of active Li+ within NMC622; no structural evolution was found for the graphite anode, even after 200 cycles under 6C (10 minutes) high charging rates. The aging behavior of liquid electrolyte was further analyzed via inductively coupled plasma-optical emission spectrometry (ICP-OES) and gas chromatography-mass spectrometry (GC-MS), increased Li+ concentration under higher charging rates and show-up of diethyl carbonate (DEC) and dimethyl carbonate (DMC) caused by transesterification both suggest faster aging/degradation of liquid electrolyte under higher charging rates.  </p> <p>Given the structural evolution of NMC622 caused by irreversible Li+ loss after long term cycling, the structural evolution of both NMC622 cathode and lithiated graphite anode were further studied via operando neutron diffraction on customized LiNi0.6Mn0.2Co0.2O2 (NMC622) || graphite cell. Via a quantitative analysis of collected Bragg peaks for NMC622 and lithiated graphite anode, we found the rate independent structural evolution of NMC622: its lattice parameters <em>a</em> and <em>c</em> are mainly determined by Li+ contents within it (<em>x</em> within Li<em>x</em>Ni0.6Mn0.2Co0.2O2) and follow the same evolution during the deintercalation process, from slowest 0.27 C charging to the fastest 4.4 C charging. For graphite intercalated compounds (GICs) formed during Li+ intercalating into graphite, the sequential phase transition from pure graphite → stage III (LiC30) → stage II (LiC12) → stage I (LiC6) phase under 0.27 C charging is consistent with previous studies. This sequential phase transition is generally maintained under increasing charging rates, and the co-existence of LiC12 phase and LiC6 was found for lithiated graphite under 4.4 C charging, mainly due to the large inhomogeneity under these high charging rates. Meanwhile, for the stage II (LiC12) → stage I (LiC6) transition, which contributes half the specific capacity for the graphite anode, quantitative analysis via Johnson-Mehl-Avrami-Kolmogorov (JMAK) model suggests it to be a diffusion-controlled, one-dimensional transition, with decreasing nucleation kinetics under increasing charging rates. </p> <p>Based on the LiC12 → LiC6 transition process, strategies to improve the Li+ transport properties were further utilized. Various cosolvents with smaller viscosity, from dimethyl carbonate (DMC), ethyl acetate (EA), methyl acetate (MA) to ethyl formate (EF), were further tested by replacing 20% (weight percent) ethyl methyl carbonate (EMC) of typical 1.2 M LiPF6 salt solvated in ethylene carbonate (EC)/EMC solvents (with a weight ratio of 30:70). From the measurement of their ion conductivity, the introduction of these cosolvents indeed enhanced the Li+ transport properties. This was further verified by improved rate performance from 2C, 3C to 4C charging for liquid electrolytes using these cosolvents. Both X-ray absorption spectroscopy (XAS) and X-ray powder diffraction (XRD) indicated the increase of Ni valence state and structural evolution of NMC622, all resulting from the irreversible loss of active Li+ within the NMC622 cathode. From long term cycling performance and further analysis of interfaces formed between electrode and anode, the best performance of electrolyte using DMC cosolvent was attributed to the most stable solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) formed during the cycling. </p>

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.

Lithium-ion batteries (LIB) represent a promising energy storage solution in the pursuit of electrification to combat climate change. In order for LIBs to be used across different industries, they have to be commercially viable. The viability for manufacturing LIBs at scale is increasing, with manufacturing costs decreasing 89% in the last ten years. However, the LIB manufacturing process is complex and can generate large amounts of scrap due to various non-conformities (NCs). Therefore, to further increase the ability to manufacture high-quality LIBs at scale, it is crucial to minimize the occurrence of NCs by understanding their root causes. This thesis examines the characteristics of one of the non-conformities occurring in the electrode coating process, namely the formation of craters on the coated surface of the anode electrode. The thesis was conducted at Northvolt Labs using a DMAIC approach to establish relationships between various process parameters and the formation of craters in two processes, coating, and its precursor process, slurry mixing. Utilizing the data models linear regression, CART regression, regularized linear regression, and a slurry experiment, process parameters and characteristics that affect crater formation were identified. Firstly, from the data models, it was distinguished that the speed of the supply pump used in transferring the slurry from the supply tank to the slot die, and the pressure in the filter pump, have the largest effect on crater formation. Further, the time that the slurry spends in storage, i.e. from a completely mixed slurry batch to it being applied in coating, affects crater formation. In this case, the longer the slurry is stored, the more craters are found. Another notable result is that refilling the coating supply tank induces crater formation. The mentioned results indicate that the various stages of slurry transfer undertaken before coating can result in advantageous conditions for craters to form. Moreover, it was discovered that changes in the loading level of the coated anode surface can indicate crater formation. The slurry experiment discovered that by contaminating the slurry with lubricant grease, NCs with similar characteristics to the crater could be generated. While not likely related to craters, this result provides valuable insights for slurry contamination. In addition to the data models and experiments, actions to facilitate future statistical analysis investigations are proposed. This thesis also proposes actions that can be undertaken to potentially mitigate the formation of craters. Suggested actions include methods to investigate the optimal storage time of the slurry before used in coating. Further, we recommend that the coating process should be monitored through the use of control charts on the loading level measurements of the coated surface. Consequently, large changes in loading level can be detected, entailing potential crater formation. We also propose adding lubricant grease as a potential risk in the PFMEA Northvolt uses for process risk evaluation. This recommendation is also complemented with suggested actions on how to handle the risks of lubricant grease contamination. / Användandet av litiumjonbatterier (LIB) som energilagring är en potentiell lösning för omställning till ett elektrifierat samhälle. Tillverkningsprocessen för LIBs är dock komplex och har en tendens att generera stora mängder kassationer på grund av olika typer av defekter. Denna studie ämnar att undersöka egenskaperna hos en av defekterna som kallas krater som kan förekomma i en av delprocesserna för litiumjonbatteritillverkning, elektrodbeläggning, där batteriets elektroder skapas genom att en blandning av aktiva material appliceras på en metallfolie. Kratern förekommer som en cirkulär form på den belagda ytan av anodelektroden. Studien genomfördes hos batteritillverkaren Northvolt Labs och använde en struktur enligt DMAIC cykeln. Syftet med studien var att fastställa samband mellan olika processparametrar och kraterformation för två olika processer, elektrodbeläggning och dess föregångare, framställning av den aktiva materialblandningen. Genom att använda datamodellerna linjär regression, CART-regression, en regulariserad linjär regression  samt ett experiment kunde processparametrar och egenskaper som påverkar kraterbildningen etableras. Resultaten från datamodellerna indikerar att varvtalet i pumpen som tillför ytbeläggningsmaskinen med den aktiva materialblandningen samt trycket i filterpumpen har den största effekten på kraterbildning. Vidare så påverkar tiden som den aktiva materialblandningen lagras innan den används i beläggningsprocessen. Resultaten indikerar att ju längre tid en aktiv materialblandning lagras, desto mer kraterbildning. Samtliga resultat som nämnts ovan anvisar att de olika stadier den aktiva materialblandningen överförs bland olika behållare och verktyg kan ge upphov till kraterbildning. Ytterligare resultat från datamodellerna indikerar att en minskad tjocklek av den belagda ytan, mätt med enheten g/cm2, kan påvisa när kratrar uppstår. Detta resultat kan härledas till att kratrarna orsakar en nedåtbuktning i den belagda ytan. Utifrån experimentet med den aktiva materialblandningen kunde det fastlås att kraterliknande defekter kunde genereras genom att kontaminera blandningen med smörjfett. Dessa defekter är sannolikt inte besläktade med kratern, men dess uppkomst ger värdefulla insikter hur kontaminering kan påverka kvaliteten på den belagda ytan. Utöver resultat från datamodellerna och experimentet så presenterar även denna studie förslag på hur framtida undersökningar av statistisk karaktär kan förbättras. Studien föreslår också konkreta åtanganden som kan genomföras med syfte att reducera kraterbildning. Detta inkluderar hur ett projekt med syfte att fastslå den optimala lagringstiden för den aktiva materialblandningen innan den används i ytbeläggningsprocessen kan utformas. Vidare rekommenderas att ytbeläggningsprocessen övervakas med hjälp av att upprätta styrdiagram för ytbeläggningens nivåförändringar. Följaktligen kan stora förändringar i ytbeläggningens jämnhet detekteras, vilket kan vara en indikator på kraterbildning. Studien rekommenderar också att tillägga kontaminering av smörjfett i den aktiva materialblandningen som en potentiell risk i Northvolts PFMEA. Denna rekommendation kompletteras även med förslag på åtanganden som kan tas för att hantera risken för kontaminering av smörjfett.

Wind resources are highly intermittent and fluctuant, making wind turbines less reliable and the unstable power output will affect grid stability and security. This paper presents an idea of integrating the solar PV plant and energy storage system into an existing wind project, project Rödene in Gothenburg. The hybrid renewable system, which consists of two or more renewable energy sources, is considered the renewable energy development trend. An economic analysis of a 1.2 MW PV plant, 5 MW lithium-ion battery storage system and 300 kg hydrogen fuel cell storge system are assessed in terms of LCOE and LCOS of plants. The revenue stream is discussed separately, consisting of electricity tariff, ancillary services and energy arbitrage. The results show that both PV plant and energy store systems are unprofitable. When the PV panel cost is reduced more than 30% and the annual production increases at least 30%, the LCOE of the PV plant arrives at the break-even point. Also result shows the hydrogen fuel cell energy storage system is too expensive of commercial use, and the battery energy storage system has a high potential of profitable if the ancillary service in Sweden is well organized in the future

NASCION-type lithium-aluminum-germanium-phosphate (LAGP) glass-ceramic is one of the most promising solid electrolyte (SEs) material for the next generation Li-ion battery. Based on the crystallization of glass-ceramic material, the two-step heat treatment was designed to control the crystallization of Li-ion conducting crystal in the glass matrix. The results show that the LAGP crystal is preferred to internally crystalize, Tg + 60%∆T is the nucleation temperature that provides the highest ion conductivity. The compositional investigation also found that, pure LAGP crystal phase can be synthesized by lowering the amount of GeO2. To fill gap of atomic structure in LAGP glass-ceramic, molecular dynamic (MD) simulation was used to build the crystal, glass, and interfacial structure LAGP. The aliovalent ion substitution induced an simultaneously redistribution of Li to the 36f interstitial site, and the rapid cooperative motion between the Li-ions at 36f can drop the activation energy of LAGP crystal by decreasing the relaxation energy; furthermore, an energy model was built based on the time-based analysis of Li-ion diffusion to articulate the behavior. The glass and interfacial structure show and accumulation of AlO4, GeO4 and Li at the interface, which explains the Li-trapping on the intergranular glass phase. An in-situ synchrotron X-ray study found that, by using two-step heat treatment, the nucleation of Li-ion conducting crystal in the glass-matrix induced large strain from interfacial tension, which can also promote the incorporation of aliovalent ion substitution in the NASICON crystal and enhances the ion conductivity.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18981号 / 工博第4023号 / 新制||工||1619(附属図書館) / 31932 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 松原 英一郎, 教授 邑瀬 邦明, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

著作権、出典、利用制限の表示を出版社より求められている。 / 京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第19824号 / エネ博第330号 / 新制||エネ||66(附属図書館) / 32860 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)准教授 高井 茂臣, 教授 萩原 理加, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM