Masters Thesis summarizes the theoretical findings about lithium-ion akumulators. It gives a overview of the basic types of galvanic cells, then deals in detail with the lithium-on cell. It's composition, electrochemical principle of working, thermal dependence, construction and area of application. The thesis describes the basic methods of measuring lithium-on cells, such as cyclic charging and discharging, cyclic voltammetry. The practical part compares selected types of materials for negative elektrodes in different temperatures.

The aim of this master´s thesis was the measurement of electrical conductivity and dynamic viscosity of the electrolytes. Based on these measurements to verify Walden theorem between measured variables. Electrolytes were used on sulfolane base in combination with propylene carbonate and salt. The thesis also deals with the measuring method of dielectric properties of electrical and optical method with a refractometer. The freezing point of combination of sulfolan and propylene carbonate were determined by cryoscopy.

This master´s thesis deals with electrodes for lithium-ions batteries based on LiCoO2. The first part of the project is devoted to the characteristics of Li-ion batteries, electrochemical reactions and characteristics of electrode materials. The next part describes an experiment that deals with the effects of NA doping on performance of layered materials for lithium secondary batteries. The materials were measured by cyclic voltammetry, impedance spectroscopy and galvanostatic cycling.

This diploma thesis deals with materials used by production ofcathodes of Lithium-ion batteries. Primary this thesis deals with LiCoO2material and its subsidizing of alkali metals. The first part deals with the charakteristic of Lithium-ion batteries, used materials, possibilities of doping and charging. The practical part concentrates on production of active substance of cathode and doping this substance by sodium and potassium. The methods of evaluation were used galvanostaticcycling and x-ray analysis (XRD).

Department of Chemistry / As an alternative energy source, lithium ion batteries have become increasingly important with a wide range of applications in industry, and many international companies are investing in this big project. This study was aimed at the development of safer lithium-ion power sources by using new organic additives to overcome the possible safety problems. In this study, the conformations and energies of several synthesized boronates were investigated through computational study using density functional theory (DFT) with the Becke’s three-parameter hybrid method utilizing the Lee-Young-Parr correlation functional (B3LYP). After initial energy optimization using Møller-Plesset Perturbation theory (MP2), the conformational preferences and energetics in vacuo were investigated using DFT calculations and the 6-31G(d,p) basis set. Subsequently, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the compounds in terms of their usefulness as electrolyte additives. At least two of these show excellent promise for use in lithium-ion batteries.

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

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>