An ever-decreasing cost of photovoltaics (PV) combined with generous installation subsidies lead to a growth of PV systems in Sweden. A large-scale penetration of PV power would make Energy Storage Systems (ESS) interesting for providing back-up storage, enabling flexibility and regulating intermittence. ESS represents a vital link between electrical supply and demand, and moreover a critical feature for increasing the use and attractiveness of renewable and intermittent energy sources. The purpose of this study is to do a quantitative analysis examining the most beneficial way to store electricity from PV regarding investment cost, life span, capacity and pay-off time. The study object is Valsätraskolan, a school in Uppsala with an existing PV system. The thesis shows that Lithium-ion batteries are the best prospected battery type but still not an economically profitable investment. With the current grid- and battery prices the most suitable battery solution has a pay-off time of 125 years. If the school would extend their PV system to cover all preferable roof areas, the pay-off time would be 48 years. If ESS are to become attractive from a financial point of view, the grid prices would have to increase and the cost for ESS decrease substantially.

Rechargeable lithium-ion batteries are now attracting great attention for applications in portable electronic devices and electrical vehicles, because of their high energy density, long cycle and great convenience. For new generations of rechargeable lithium-ion batteries, they applied not only to consumer electronics but also especially to clean energy storage and hybrid electric vehicles. Therefore, further breakthroughs in electrode materials that open up a new important avenue are essential. Graphite, the most commonly used commercial anode material, has a limited reversible lithium intercalation capacity (372 mAh g-1). In this regard, tremendous efforts have been made towards even further improving high capacity, excellent rate capability, and cycling stability by developing advanced anode materials. This work focuses on the lithium storage properties of nickel oxide (NiO) and germanium (Ge) nanomembranes anodes mainly fabricated by electron-beam evaporation. Specifically, NiO is selected for conversion-type material because of high theoretical specific capacity of 718 mAh g-1 and easily obtained material. The resultant curved NiO nanomembranes anodes exhibit ultrafast power rate of 50 C (1 C = 718 mA g-1) and good capacity retention (721 mAh g-1, 1400 cycles). Remarkably, multifunctional Ni/NiO hybrid nanomembranes were further fabricated and investigated. Benefiting from the advantages of the intrinsic architecture and the electrochemical catalysis of metallic nickel, the hybrid Ni/NiO anodes could be tested at an ultrahigh rate of ~115 C. With Ge as active alloying-type material (1624 mAh g-1), the effect of the incorporated oxygen to the lithium storage properties of amorphous Ge nanomembranes is well studied. The oxygen-enabled Ge (GeOx) nanomembranes exhibit improved electrochemical properties of highly reversible capacity (1200 mAh g-1), and robust cycling performance.

Batteries are promising sources of green and sustainable energy that have been widely used in various applications. Lithium-ion batteries (LIBs) have an important role in the energy storage sector due to its high specific energy and energy density relative to other rechargeable batteries. The main challenges for keeping the LIBs to work under safe conditions, and at high performance are strongly related to the battery thermal management. In this study, a critical literature review is first carried out to present the technology development status of the battery thermal management system (BTMS) based on air and liquid cooling for the application of battery energy storage systems (BESS). It was found that more attention has paid to the BTMS for electrical vehicle (EV) applications than for stationary BESS. Even though the active forced air cooling is the most commonly used method for stationary BESS, limited technical information is available. Liquid cooling has widely been used in EV applications with different system configurations and cooling patterns; nevertheless, the application for BESS is hard to find in literature.To ensure and analyze the performance of air and liquid cooling system, a battery and thermal model developed to be used for modeling of BTMS. The models are based on the car company BMW EV battery pack, which using Nickel Manganese Cobalt Oxide (NMC) prismatic lithium-ion cell. Both air and liquid cooling have been studied to evaluate the thermal performance of LIBs under the two cooling systems.According to the result, the air and liquid cooling are capable of maintaining BESS under safe operation conditions, but with considering some limits. The air-cooling is more suitable for low surrounding temperature or at low charging/discharge rate (C-rate), while liquid cooling enables BESS to operate at higher C-rates and higher surrounding temperatures. However, the requirement on the maximum temperature difference within a cell will limits the application of liquid cooling in some discharge cases at high C-rate. Finally, this work suggests that specific attention should be paid to the pack design. The design of the BMW pack is compact, which makes the air-cooling performance less efficient because of the air circulation inside the pack is low and liquid cooling is more suitable for this type of compact battery pack.

Les batteries lithium-ion sont présentement d’excellentes candidates pour le stockage électrochimique d’énergie du futur. Cela dit, les batteries lithium-métal pourraient présenter des propriétés électrochimiques encore plus avantageuses. Cependant, ces types de batteries présentent encore des inconvénients, notamment au niveau de leur sécurité. Un des responsables majeurs de ceux-ci est l’électrolyte liquide organique. Parmi les différentes voies exploitables pour améliorer la sécurité de ces technologies, les électrolytes solides polymères (SPE) sont largement étudiés. Classiquement, ces systèmes sont mis en forme en présence de solvants qui sont ensuite évaporés. Aussi, lorsque le processus d’évaporation de solvants est terminé, les échantillons sont habituellement réexposés à l’air ambient. Or, d’une part, malgré le séchage important d’un échantillon, il se peut qu’il reste du solvant de mise en forme résiduelle. D’autre part, l’eau atmosphérique peut s’infiltrer au sein de celui-ci. Cependant, ce ne sont pas des facteurs qui sont considérés dans la recherche présente dans le domaine. Bien que l’influence des solvants résiduels est parfois mentionnée, elle n’est jamais quantifiée de façon convenable, et cela reste un facteur mal compris et souvent omis. Dans cette étude, des échantillons de différents types de SPE ont été préparés selon des conditions standards, leur teneur en solvants résiduels a été contrôlée et analysée par différentes méthodes développées au cours de cette recherche. Pour la quantification de l’eau, un analyseur d’humidité spécifique a été utilisé, et il a été montré que l’eau résiduelle permet d’augmenter les conductivités ioniques des échantillons. Pour la quantification des solvants résiduels organiques, une méthode analytique employant la chromatographie gazeuse couplée à la spectrométrie de masse a été développée. Il a été observé que comme avec l’eau, les solvants résiduels augmentent la conductivité ionique des échantillons étudiés. Cette étude doit montrer aux chercheurs dans le domaine que le contrôle des solvants résiduels est un facteur primordial dans le développement des SPEs, et que c’est un paramètre qui doit être systématiquement évalué. / Lithium-ion batteries are today’s candidates for future long-term electrochemical storage of renewable energies. That said, lithium-metal batteries could offer even more appealing electrochemical properties. However, both types of batteries still suffer from certain technical difficulties such as safety. One of the culprits for their reduced safety is the use of an organic liquid electrolyte. Indeed, the latter is flammable and poses a risk, as numerous battery fire accidents have shown throughout the past years. Luckily, scientific research has been able to propose safer alternatives to liquid electrolytes applicable to lithium batteries by replacing the former by solid state electrolytes. Amongst these systems, solid polymer electrolytes (SPE) can be considered as a promising possibility to eliminating the safety issues. Conventionally, SPEs are prepared in a solvent that is evaporated at the end of the manufacturing. Additionally, atmospheric humidity can infiltrate these materials and alter their properties. However, residual solvent content is seldom mentioned, and even when it is, the specific experimental parameters are lacking which makes it a misunderstood and regularly omitted factor in battery performance evaluation. In this study, residual solvents are quantified in different SPE systems that are prepared according to standard and non-standard procedures. To do so, certain samples have had their solvent content artificially modified in order to control and analyse it. Firstly, water content is assessed using a specific moisture analyser. Secondly, an analytical method employing gas chromatography coupled to mass spectrometry has been developed to determine the residual SPE processing solvent. It has been concluded that, similarly to water, residual solvents also contribute to enhancing ionic conductivities of SPEs. Hopefully, this study will shed light on the importance of controlling residual solvent content in SPEs, and the necessity of systematically assessing that parameter.

Die untersuchten Ausgangsmaterialien α-Fe2U3, ɣ-Fe2O3, Fe3O4, CoO, Co3O4, NiO sowie CuO eignen sich durch ihre hohe theoretische spezifische Kapazität als Elektrodenmaterial für Lithium-Ionen-Batterien. Die zugrundeliegenden Mechanismen zur Speicherung der Li-Ionen konnten mit allen Phasenumwandlungen und der Bildung von Zwischenprodukten im ersten Reduktionsschritt beschrieben werden. In Abhängigkeit von der Kristallstruktur der Ausgangsmaterialien und den Reaktionsgeschwindigkeiten konnten der Gesamtreaktion die einzelnen Mechanismen Interkalation von Li-Ionen, Substitution von Kationen in der Kristallstruktur und Konversionsmechanismus zugeordnet werden. Auf Grund des gemeinsamen kubisch flächenzentrierten Sauerstoffuntergitters der Ausgangsmaterialien und Zwischenprodukte zeigen sich für die Materialsysteme Fe-O, Co-O und Ni-O Orientierungsbeziehungen zwischen den Kristalliten des Ausgangsoxids, des lithiierten Metalloxids und der Li2O-Matrix. Im Gegensatz dazu sind die auf der CuO-Phase basierenden Kristallite regellos orientiert und zeigen eine höhere Zyklenstabilität. Die Orientierungsbeziehung zwischen den lithiierten Metalloxiden und der Li2O-Matrix hindert dagegen den Austausch der Li-Ionen, beeinträchtigt die Zyklenstabilität und trägt so zu einer schnelleren Alterung der Elektrode bei.

Indiana University-Purdue University Indianapolis (IUPUI) / Rechargeable lithium ion batteries are widely used in portable consumer electronics such as cellphones, laptops, etc. These batteries are capable to provide high energy density with no memory effect and they have small self-discharge when they are not in use, which increases their potential for future electric vehicles. Investigators are attempting to improve the performance of these cells by focusing on the energy density, cost, safety, and durability. The energy density improves with high operation voltage and high capacity. Before any further development of high voltage materials, safe electrolytes with high ionic conductivity, wide electrochemical window, and high stability with both electrodes need to be developed. In this thesis a new strategy was investigated to develop electrolytes that can contribute to the further development of battery technology. The first study is focused on preparing a hybrid electrolyte, the combination of inorganic solid and organic liquid, for lithium based rechargeable batteries to illustrate the effect of electrode/electrolyte interfacing on electrochemical performance. This system behaves as a self-safety device at higher temperatures and provides better performance in comparison with the solid electrolyte cell, and it is also competitive with the pure liquid electrolyte cell. Then a multilayer electrolyte cell (MEC) was designed and developed as a new tool for investigating electrode/electrolyte interfacial reactions in a battery system. The MEC consists of two liquid electrolytes (L.E.) separated by a solid electrolyte (S.E.) which prevents electrolyte crossover while selectively transporting Li+ ions. The MEC successfully reproduced the performance of LiFePO4 comparable with that obtained from coin cells. In addition, the origin of capacity fading in LiNi0.5Mn1.5O4full-cell (with graphite negative electrode) was studied using the MEC. The performance of LiNi0.5Mn1.5O4 MEC full-cell was superior to that of coin full-cell by eliminating the Mn dissolution problem on graphite negative electrode as evidenced by transmission electron microscopy (TEM) analysis. The MEC can be a strong tool for identifying the electrochemical performances of future high voltage positive electrode materials and their electrode/electrolyte interfacial reactions. Finally, by employing the multilayer electrolyte concept, a new application will be introduced to recycle the lithium. This study demonstrates the feasibility of using water and the contents of waste Li-ion batteries for the electrodes in a Li-liquid battery system. Li metal was collected electrochemically from a waste Li-ion battery containing Li-ion source materials from the battery’s anode, cathode, and electrolyte, thereby recycling the Li contained in the waste battery at the room temperature.

Indiana University-Purdue University Indianapolis (IUPUI) / The prevalent applications of energy storage devices have incited wide-spread efforts on production of thin, flexible, and light-weight lithium-ion batteries. In this work, lithium-ion batteries using novel flexible paper-based current collectors have been developed. The paper-based current collectors were fabricated from carbon nanotube (CNT)-coated wood microfibers (CNT-microfiber paper). This thesis presents the fabrication of the CNT-microfiber paper using wood microfibers, coating electrode materials, design and assemblies of battery, testing methodologies, and experimental results and analyses. Wood microfibers were coated with carbon nanotubes and poly(3,4-ethylenedioxythiophene) (PEDOT) through an electrostatic layer-by-layer nanoassembely process and formed into a sheet, CNT-microfiber paper. The CNT loading of the fabricated paper was measured 10.1 μg/cm2 subsequently considered. Electrode material solutions were spray-coated on the CNT-microfiber paper to produce electrodes for the half and full-cell devices. The CNT current collector consists of a network structure of cellulose microfibers at the micro-scale, with micro-pores filled with the applied conductive electrode materials reducing the overall internal resistance for the cell. A bending test revealed that the paper-based electrodes, compared to metal ones, incurred fewer damages after 20 bends at an angle of 300o. The surface fractures on the paper-based electrodes were shallow and contained than metallic-based electrodes. The micro-pores in CNT-microfiber paper structure provides better adherence to the active material layer to the substrate and inhibits detachment while bending. Half-cells and full-cells using lithium cobalt oxide (LCO), lithium titanium oxide (LTO), and lithium magnesium oxide (LMO) were fabricated and tested. Coin cell assembly and liquid electrolyte was used. The capacities of half-cells were measured 150 mAh/g with LCO, 158 mAh/g with LTO, and 130 mAh/g with LMO. The capacity of the LTO/LCO full-cell also was measured 126 mAh/g at C/5 rate. The columbic efficiency of the LTO/LCO full-cell was measured 84% for the first charging cycle that increased to 96% after second cycle. The self-discharge test of the full-cell after charging to 2.7 V at C/5 current rate is showed a stable 2 V after 90 hours. The capacities of the developed batteries at lower currents are comparable to the metallic electrode-based devices, however, the capacities were observed to drop at higher currents. This makes the developed paper-based batteries more suitable for low current applications, such as, RFID tags, flexible electronics, bioassays, and displays. The capacities of the batteries at higher current can be improved by enhancing the conductivity of the fibers, which is identified as the future work. Furthermore, fabrication of an all solid state battery using solid electrolyte is also identified as the future work of this project.

Indiana University-Purdue University Indianapolis (IUPUI) / A gradient free function optimization technique, namely particle swarm optimization (PSO) algorithm, is utilized in parameter identification of the electrochemical model of a Lithium-Ion battery having a LiCoO2 chemistry. Battery electrochemical model parameters are subject to change under severe or abusive operating conditions resulting in, for example, Navy over-discharged battery, 24-hr over-discharged battery, and over-charged battery. It is important for a battery management system to have these parameters changes fully captured in a bank of battery models that can be used to monitor battery conditions in real time. In this work, PSO methodology has been used to identify four electrochemical model parameters that exhibit significant variations under severe operating conditions. The identified battery models were validated by comparing the model output voltage with the experimental output voltage for the stated operating conditions. These identified conditions of the battery were then used to monitor condition of the battery that can aid the battery management system (BMS) in improving overall performance. An adaptive estimation technique, namely multiple model adaptive estimation (MMAE) method, was implemented for this purpose. In this estimation algorithm, all the identified models were simulated for a battery current input profile extracted from the hybrid pulse power characterization (HPPC) cycle simulation of a hybrid electric vehicle (HEV). A partial differential algebraic equation (PDAE) observer was utilized to obtain the estimated voltage, which was used to generate the residuals. Analysis of these residuals through MMAE provided the probability of matching the current battery operating condition to that of one of the identified models. Simulation results show that the proposed model based method offered an accurate and effective fault diagnosis of the battery conditions. This type of fault diagnosis, which is based on the models capturing true physics of the battery electrochemistry, can lead to a more accurate and robust battery fault diagnosis and help BMS take appropriate steps to prevent battery operation in any of the stated severe or abusive conditions.

This thesis proposes, validates, and compares low-complexity algorithms for the fast-and-safe charge and balance of Li-ion batteries both for the single cell case and for the case of a serially-connected string of battery cells. The proposed algorithms are based on a reduced-order electrochemical model (Equivalent Hydraulic Model, EHM), and make use of constrained-control strategies to limit the main electrochemical degradation phenomena that may accelerate aging, namely: Lithium plating in the anode and solvent oxidation inthe cathode. To avoid the computational intensiveness of solving an online optimization as in the Model Predictive Control (MPC) framework, this thesis proposes the use of Reference Governor schemes. Variants of both the Scalar Reference Governors (SRG) and the Explicit Reference Governors (ERG) are developed to deal with the non-convex admissible region for the charge of a battery cell, while keeping a low computational burden. To evaluate the performance of the proposed techniques for the single cell case, they are experimentallyvalidated on commercial Turnigy LCO cells of 160 mAh at four different constant temperatures (10, 20, 30 and 40 °C). In the second part of this thesis, the proposed charging strategies are extended to take into account the balance of a serially-connected string of cells. To equalize possible mismatches, a centralized policy based on a shunting grid (active balance) connects or disconnects the cells during the charge. After a preliminary analysis, a simple mixed-integer algorithm was proposed. Since this method is computationally inefficient due to the high number of scenarios to be evaluated, this thesis proposes a ratio-based algorithm based on a Pulse-Width Modulation (PWM) approach. This approach can be used within both MPC and RG schemes. The numerical validations of the proposed algorithms for the case of a string of four battery cells are carried out using a simulator based on a full-order electrochemical model. Numerical validations show that the PWM-like approach charges in parallel all the cells within the pack, whereas the mixed-integer approach charges the battery cells sequentially from the battery cell with the lowest state of charge to the ones with the highest states of charge. On the basis of the simulations, an algorithm based on a mixed logic that allows to charge in a “sequential parallel” approach is proposed. Some conclusions and future directions of research are proposed at the end of the thesis. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Electric vehicles have received substantial attention in the past few years since they provide a more sustainable, efficient, and greener transportation alternative in comparison to conventional fossil-fuel powered vehicles. Lithium-Ion batteries represent the most important component in the electric vehicle powertrain and thus require accurate monitoring and control. Many challenges are still facing the mass market production of electric vehicles; these challenges include battery cost, range anxiety, safety, and reliability. These challenges can be significantly mitigated by incorporating an efficient battery management system. The battery management system is responsible for estimating, in real-time, the battery state of charge, state of health, and remaining useful life in addition to communicating with other vehicle components and subsystems. In order for the battery management system to effectively perform these tasks, a high-fidelity battery model along with an accurate, robust estimation strategy must work collaboratively at various power demands, temperatures, and states of life. Lithium ion batteries are considered in this research. For these batteries, electrochemical models represent an attractive approach since they are capable of modeling lithium diffusion processes and track changes in lithium concentrations and potentials inside the electrodes and the electrolyte. Therefore, electrochemical models provide a connection to the physical reactions that occur in the battery thus favoured in state of charge and state of health estimation in comparison to other modeling techniques. The research presented in this thesis focuses on advancing the development and implementation of battery models, state of charge, and state of health estimation strategies. Most electrochemical battery models have been verified using simulation data and have rarely been experimentally applied. This is because most electrochemical battery model parameters are considered proprietary information to their manufacturers. In addition, most battery models have not accounted for battery aging and degradation over the lifetime of the vehicle using real-world driving cycles. Therefore, the first major contribution of this research is the formulation of a new battery state of charge parameterization strategy. Using this strategy, a full-set of parameters for a reduced-order electrochemical model can be estimated using real-world driving cycles while accurately calculating the state of charge. The developed electrochemical model-based state of charge parameterization strategy depends on a number of spherical shells (model states) in conjunction with the final value theorem. The final value theorem is applied in order to calculate the initial values of lithium concentrations at various shells of the electrode. Then, this value is used in setting up constraints for the optimizer in order to achieve accurate state of charge estimation. Developed battery models at various battery states of life can be utilized in a real-time battery management system. Based on the developed models, estimation of the battery critical surface charge using a relatively new estimation strategy known as the Smooth Variable Structure Filter has been effectively applied. The technique has been extended to estimate the state of charge for aged batteries in addition to healthy ones. In addition, the thesis introduces a new battery aging model based on electrochemistry. The model is capable of capturing battery degradation by varying the effective electrode volume, open circuit potential-state of charge relationship, diffusion coefficients, and solid-electrolyte interface resistance. Extensive experiments for a range of aging scenarios have been carried out over a period of 12 months to emulate the entire life of the battery. The applications of the proposed parameterization method combined with experimental aging results significantly improve the reduced-order electrochemical model to adapt to various battery states of life. Furthermore, online and offline battery model parameters identification and state of charge estimation at various states of life has been implemented. A technique for tracking changes in the battery OCV-R-RC model parameters as battery ages in addition to estimation of the battery SOC using the relatively new Smooth Variable Structure Filter is presented. The strategy has been validated at both healthy and aged battery states of life using driving scenarios of an average North-American driver. Furthermore, online estimation of the battery model parameters using square-root recursive least square (SR-RLS) with forgetting factor methodology is conducted. Based on the estimated model parameters, estimation of the battery state of charge using regressed-voltage-based estimation strategy at various states of life is applied. The developed models provide a mechanism for combining the standalone estimation strategy that provide terminal voltage, state of charge, and state of health estimates based on one model to incorporate these different aspects at various battery states of life. Accordingly, a new model-based estimation strategy known as the interacting multiple model (IMM) method has been applied by utilizing multiple models at various states of life. The method is able to improve the state of charge estimation accuracy and stability, when compared with the most commonly used strategy. This research results in a number of novel contributions, and significantly advances the development of robust strategies that can be effectively applied in real-time on-board of a battery management system. / Thesis / Doctor of Philosophy (PhD)