Lithium ion batteries (LIBs) are crucial for modern electronics and electric vehicles (EV). However,their electrochemical performance is facing challenges at low temperatures (e.g ≤ 0 °C) due to reducedLi+ kinetics and increased charge-transfer resistance. Given the growing dependence on LIBs for bothelectronics and EVs, especially in cold environments, it is imperative to address the low-temperaturelimitations. Thus, improving the low-temperature performance of LIBs is essential for the broaderadoption and further advancement of LIBs. To address these challenges, this thesis demonstrates thatsignificant improvement of electrochemical performance at low temperatures can be achieved by in-corporating Lithium difluoro(oxalato)borate (LiDFOB) as an additive into the baseline electrolyte forthe Li(Ni0.8Mn0.1Co0.1)O2(NMC811)∥Li cell.At a low temperature of -20 °C, the NMC811∥Li cell with the electrolyte containing 4 wt% LiDFOBexhibited an impressive discharge capacity of 125 mAh/g at 0.1C (1C = 2.0 mAh cm−2), representingabout 61.6% of the capacity delivered at 20 °C. In contrast, the cell with the baseline electrolyte de-livered negligible discharge capacity under the same conditions. This result emphasizes the functionsof LiDFOB as an electrolyte additive in enhancing the low-temperature performance of NMC811∥Licells. This work reveals the kinetics bottleneck of Li+ transport during charge/discharge processes atlow temperatures can be mitigated by tuning cathode-electrolyte interphase (CEI) through introducingadditive into the baseline electrolyte.To substantiate these findings, Electrochemical Impedance Spectroscopy (EIS) was employed to re-veal the significant decrease of interface resistance resulting from the addition of LiDFOB into thebase electrolyte. X-ray Photoelectron Spectroscopy (XPS) further confirmed the benefits of LiDFOB,indicating that a B-rich, more conductive and thinner CEI formed on the NMC811 cathode induced byLiDFOB. The results indicate that the inclusion of LiDFOB in the baseline electrolyte is advantageousin tuning CEI at the cathode for reducing charge-transfer resistance and enhancing electrochemicalperformance.In conclusion, the tuned CEI induced by LiDFOB additive plays an important role in improving thelow-temperature performance of the NMC811∥Li cells. This improvement in the capacity delivery at-20 °C can be attributed to the formation of a highly conductive and uniform and thinner CEI layer,which in turn facilitates reduced charge-transfer resistance at low temperatures. This work sheds newlight on the electrolyte design with additives to develop high-performance LIBs operating at extremeconditions.2

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This thesis investigates several approaches to the development of high-performance batteries. A general background to the field and an introduction to the experimental methods used are given in Chapters 1 and 2 respectively. Chapter 3 presents a study of ordered and disordered LiNi₀.₅Mn₁.₅O₄ materials produced using an optimised resorcinol-formaldehyde gel (R-F gel) synthetic technique. Both materials exhibited good electrochemical properties and minimal side reaction with the electrolyte. Structural analyses of the materials in various states of discharge and charge were undertaken, and from these the charge / discharge processes were elucidated. In chapter 4 R-F gel synthesised Li(Ni₁/₃Mn₁/₃Co₁/₃)O₂ is studied and found to exhibit a high degree of structural stability on cycling, as well as excellent capacity, cyclability and rate capability. Photoelectron spectroscopy studies revealed that the R-F gel derived particles have highly stable surfaces. A discussion of the results and their significance, with particular regard to the outstanding electrochemical performance observed, is also presented. Chapter 5 sets out an investigation into the nature of R-F gel synthesised 0.5Li₂MnO₃:0.5LiNi₁/₃Mn₁/₃Co₁/₃O₂. The electrochemical data revealed that, after an initial activation stage, the R-F gel derived material exhibited a high capacity, good cyclability and exceptional rate capability. This chapter also considers some initial structural investigations and the electrochemical processes occurring on charge. In chapter 6 the use of ether-based electrolytes, combined with various cathode materials, in lithium-oxygen batteries is examined. The formation of decomposition products was observed, and a scheme suggesting probable reaction pathways is given. It was noted that significant quantities of the desired discharge product, lithium peroxide, were formed on the 1st cycle discharge, implying some electrolyte / cathode combinations do demonstrate a degree of stability. A summary of the results and a discussion of their significance are also included.

Batteries have imparted momentum to the process of transition towards a green future. However, mass application of batteries is obstructed due to their explosive nature, a trait specific to Li-Ion batteries. To cater to an efficient battery utilization, an introduction of a battery management system would provide an ultimate solution. This thesis deals with different aspects crucial in designing a battery management system for high energy as well as high power applications. To build a battery management system capable of predicting battery behavior, it is necessary to analyze the dynamic processes happening inside the battery. Hence, a battery equivalent circuit model is proposed in this thesis as well as proper analysis is done in MATLAB to project a generic structure applicable to all Li-Ion chemistries. The model accounts for all dynamic characteristics of a battery including non-linear open circuit voltage, discharge current and capacity. Effect of temperature is also modeled using a cooling system. The model is validated with test current profiles. Less than 0.1% error between measured and simulated voltage profiles indicates the effectiveness of the proposed model to predict the runtime behavior of the battery. Furthermore, the model is implemented with the energy as well as the power battery pack. State of charge calculations are performed using the proposed model and the coulomb counting method and the results indicate only a 4% variance. Therefore, the proposed model can be applied to develop a real-time battery management system for accurate battery states estimation.

Conducting polymer hydrogels (CPHs) is a class of unique materials that synergize the advantages of conducting polymers (CPs) and polymer hydrogels together. It has been employed in many high-performance electrochemical devices for years, such as energy storage and biosensors. However, large limitations of applying CPHs into the abovementioned areas have been facing the researcher for a long time, mainly due to the difficulties from complicated materials synthesis and untenable nanostructures for potential applications. The drawbacks of previously reported CPHs have put numerous disadvantages onto their applications, partially because they have, for example, high prices, untunable microscale or nanoscale architectures, environmentally hazardous properties, and unscalable and time-consuming synthesis processes. In this thesis, we proposed a novel route for carrying out CPHs by one-step organics synthesis at ambient conditions. The CPHs have hierarchically porous nanostructures crosslinked in a three-dimensional (3D) way, which enable its stable mechanical, unique chemical and physical properties, and outstanding electrochemical properties for potential applicability in long-term energy storage devices and highly sensitive biosensors. With highly controllable nanostructures of the CPHs, our novel concept and material system could possibly be utilized in a broad range of electrochemical applications, including but not limited to lithium-ion batteries (LIBs) electrodes, electrochemical capacitors (ECs), biofuel cells, medical electrodes, printable electronic devices, and biosensors. / text

This thesis provides an insight into battery modeling in electric vehicles which includes degradation mechanisms as in automotive operation in electric vehicles. As electric vehicles with lithium ion batteries increase in popularity there is an increased need to study and model the capacity losses in such batteries. If there is a good understanding of the phenomena involved and an ability to predict these losses there is also a foundation to take measures to minimize these losses. In this thesis a battery model for lithium ion batteries which includes heat dissipation is used as groundwork. This model is expanded with the addition of capacity losses due to usage as well as storage. By combining this with a simple vehicle model one can use these models to achieve an understanding as to how a battery or pack of several batteries would behave in a specific driving scenario. Much of the focus in the thesis is put into comparing the different factors of degradation to highlight what the major contributors are. The conclusion is drawn that heat is the main cause for degradation for batteries in electric vehicles. This applies for driving usage as well as during storage. As heat is generated when a battery is used, the level of current is also a factor, as well as in which state of charge region the battery is used.

Lithium-ion batteries are today finding use in automobiles aiming at reducing fuel consumption and emissions within transportation. The requirements on batteries used in vehicles are high regarding performance and lifetime, and a better understanding of the interior processes that dictate energy and power capabilities is a key to strategic development. This thesis concerns aging in lithium-ion cells using electrochemical tools to characterize electrode and electrolyte properties that affect performance and performance loss in the cells.   A central difficulty regarding battery aging is to manage the coupled effects of temperature and cycling conditions on the various degradation processes that determine the lifetime of a cell. In this thesis, post-mortem analyses on harvested electrode samples from small pouch cells and larger cylindrical cells aged under different conditions form the basis of aging evaluation. The characterization is focused on electrochemical impedance spectroscopy (EIS) measurements and physics-based EIS modeling supported by several material characterization techniques to investigate degradation in terms of properties that directly affect performance. The results suggest that increased temperature alter electrode degradation and limitations relate in several cases to electrolyte transport. Variations in electrode properties sampled from different locations in the cylindrical cells show that temperature and current distributions from cycling cause uneven material utilization and aging, in several dimensions. The correlation between cell performance and localized utilization/degradation is an important aspect in meeting the challenges of battery aging in vehicle applications.   The use of in-situ nuclear magnetic resonance (NMR) imaging to directly capture the development of concentration gradients in a battery electrolyte during operation is successfully demonstrated. The salt diffusion coefficient and transport number for a sample electrolyte are obtained from Li+ concentration profiles using a physics-based mass-transport model. The method allows visualization of performance limitations and can be a useful tool in the study of electrochemical systems. / <p>QC 20140512</p>

"Lithium ion batteries have dominated the portable electronics market and have the potential to dominate large-scale battery applications including hybrid and electric vehicles, as well as grid storage, because of their high energy and power densities1,2. It is well known that conventional electrolytes show poor anodic stabilities above 4.5 V versus Li/Li+.3 As a result, high voltage electrolytes are essential for the development of next generation high energy lithium ion batteries. Both fluorinated electrolytes and additives can be introduced into the electrolyte system.4 In this work, fluorinated electrolytes were used in both graphite-LiNi0.5Co0.2Mn0.3O2 (NCM523) (operated between 3.0 - 4.6 V) and graphite- LiNi0.5Mn1.5O4 (LNMO) (operated between 3.5 - 4.9 V) full cell systems. The baseline electrolyte for all cells (referred to as Gen2) was composed of 1.2M LiPF6 dissolved in a mixture of EC and EMC (3:7 in weight ratio). After a series of electrochemical tests, compared to the baseline electrolyte, the fluorinated electrolytes displayed significantly enhanced performance under both high cut off voltage and high temperature (55 oC). The post test analysis results showed that the cycled electrode can not only reach a much more stable interface but also overcome the crystal structure change after long term cycling when the fluorinated electrolyte system was used. In addition to changing the solvent, a series of additives were designed, synthesized and evaluated for high-voltage Li-ion battery cells using a Ni-rich layered cathode materials LiNi0.5Co0.2Mn0.3O2 (NCM523). The repeated charge/discharge cycling for NCM523/graphite full cells using Gen2 with 1 wt % of these additives as electrolytes was performed. Electrochemical performance testing and post analysis result demonstrated that our as selected or designed cathode additives could passivate the cathode and prevent the cathode from side reactions. The developed methodology could provide fundamental direction in the design and investigation of better electrolytes for the next generation lithium ion batteries."

<p>U ovoj doktorskoj disertaciji ispitivani su elektroliti na bazi jonskih tečnosti pogodni za<br />primenu u litijum&nbsp; jonskim baterijama. Fizičko-hemijska svojstva binarnih sme&scaron;a<br />jonskih tečnosti sa dicijanamidnim i bis(trifluorometilsulfonil)imidnim anjonima i<br />molekulskih rastvarača ispitana su u celom opsegu molskih udela i na različitim<br />temperaturama. Na osnovu izmerenih gustina, viskoznosti i električne provodljivosti<br />izračunati su različiti fizičko hemijski parametri i diskutavne interakcije između komponenata sme&scaron;a. Ispitana je termička i elektrohemijska stabilnost odabranih<br />elektrolita. Dodatkom litijumove soli u odabrane binarne sme&scaron;e dobijeni su ternarni<br />sistemi koji su okarakterisani u zavisnoti od koncentracije litijumove soli. Odabrani<br />elektroliti upotrebljeni su za&nbsp; ispitivanje performansi litijum&nbsp; jonske ćelije sa anatas<br />TiO2&nbsp; nanotubularnim elektrodama.Cikličnom voltametrijom i galvanostatskim<br />cikliranjem su ispitane performanse ćelije u toku 150 ciklusa punjenja i pražnjenja. Na<br />osnovu ciklovoltametrijskih merenja izračunati su koeficijenti difuzije i energija aktivacije za difuziju.</p> / <p>In this doctoral dissertation, Ion liquid-based electrolytes were tested for use in&nbsp; lithium-ion batteries. The physicochemical properties of binary mixtures of ionic&nbsp; liquids with dicyanamide and bis (trifluoromethylsulfonyl) imide anions and&nbsp; molecular solvents were examined throughout the range of molar proportions and at different temperatures. Based on the measured densities, viscosity and electrical conductivity, various physical chemical parameters and discrete interactions between&nbsp; the components of the mixture are calculated. Thermal and electrochemical stability of selected electrolytes was examined. By addition of lithium salt to the selected binary mixtures, ternary systems were characterized which were characterized by the concentration of lithium salt. The selected electrolytes were used to test the performance of the lithium-ion cell with anatomic TiO2 nanotubular electrodes. Cyclic voltammetry and galvanostatic cycling tested the cell&#39;s performance during the 150 charge and discharge&nbsp; cycles. Based on cyclotoltametric&nbsp; measurements, the diffusion coefficients and activation energies for diffusion were calculated.</p>

L’accroissement des performances des accumulateurs Li-ion sur les 25 dernières années découle principalement de l’optimisation de leurs composants inactifs. Aujourd’hui, l’urgence environnementale impose de développer de nouveaux matériaux actifs d’électrode pour proposer la prochaine génération d’accumulateur qui participera à la transition énergétique. A cet effet, le silicium pourrait avantageusement remplacer le graphite des électrodes négatives à moyen terme. Cependant la rétention de capacité des électrodes de silicium est mise à mal par l’expansion volumique que le matériau subit lors sa réaction d’alliage avec le lithium, qui mène à la déconnexion des particules de Si et à une réduction continue de l’électrolyte. Une compréhension de ces phénomènes de vieillissement à l’échelle de la nanoparticule est nécessaire à la conception d’électrodes de silicium viables. Pour ce faire, la technique STEM-EELS a été optimisée de manière à s’affranchir des problèmes d’irradiation qui empêchent l’analyse des matériaux légers d’électrode négative et de la Solid electrolyte interface (SEI), grâce à l’analyse des pertes faibles EELS. Un puissant outil de cartographie de phase est obtenu et utilisé pour mettre en lumière la lithiation cœur-coquille initiale des nanoparticules de silicium cristallin, la morphologie hétérogène et la composition de la SEI, ainsi que la dégradation du silicium à l’issue de cyclages prolongés. Enfin, un modèle de vieillissement original est proposé, en s’appuyant notamment sur un effort de quantification des mesures STEM-EELS sur un grand nombre de nanoparticules. / Over the last 25 years, the performance increase of lithium-ion batteries has been largely driven by the optimization of inactive components. With today’s environmental concerns, the pressure for more cost-effective and energy-dense batteries is enormous and new active materials should be developed to meet those challenges. Silicon’s great theoretical capacity makes it a promising candidate to replace graphite in negative electrodes in the mid-term. So far, Si-based electrodes have however suffered from the colossal volume changes silicon undergoes through its alloying reaction with Li. Si particles will be disconnected from the electrode’s percolating network and the solid electrolyte interface (SEI) continuously grows, causing poor capacity retention. A thorough understanding of both these phenomena, down to the scale of a single silicon nanoparticle (SiNP), is critical to the rational engineering of efficient Si-based electrodes. To this effect, we have developed STEM-EELS into a powerful and versatile toolbox for the study of sensitive materials and heterogeneous systems. Using the low-loss part of the EEL spectrum allows us to overcome the classical limitations of the technique.This is put to use to elucidate the first lithiation mechanism of crystalline SiNPs, revealing Li1.5Si @ Si core-shells which greatly differs from that of microparticles, and propose a comprehensive model to explain this size effect. The implications of that model regarding the stress that develops in the crystalline core of SiNPs are then challenged via stress measurements at the particle scale (nanobeam precession electron diffraction) for the first time, and reveal enormous compressions in excess of 4±2 GPa. Regarding the SEI, the phase-mapping capabilities of STEM-EELS are leveraged to outline the morphology of inorganic and organic components. We show that the latter contracts during electrode discharge in what is referred to as SEI breathing. As electrodes age, disconnection causes a diminishing number of SiNPs to bear the full capacity of the electrode. Overlithiated particles will in turn suffer from larger volumes changes and cause further disconnection in a self-reinforcing detrimental effect. Under extreme conditions, we show that SiNPs even spontaneously turn into a network of thin silicon filaments. Thus an increased active surface will compound the reduction of the electrolyte and the accumulation of the SEI. This can be quantified by summing and averaging STEM-EELS data on 1104 particles. In half-cells, the SEI volume is shown to increase 4-fold after 100 cycles without significant changes in its composition, whereas in full cells the limited lithiation performance understandably leads to a mere 2-fold growth. In addition, as the operating potential of the silicon electrodes increases in full cells – potential slippage – organic products in the SEI switch from being carbonate-rich to oligomer-rich. Finally, we regroup these findings into an extensive aging model of our own, based on both local STEM-EELS analyses and the macro-scale gradients we derived from them as a whole.