Temperature is one of the most important parameters for the performance, safety, and aging of lithium-ion batteries and has been linked to all main barriers for widespread commercial success of electric vehicles. The aim of this thesis is to highlight the importance of temperature effects, as well as to provide engineering tools to study these. The mass transport phenomena of the electrolyte with LiPF6  in EC:DEC was fully characterized in between 10 and 40 °C and 0.5 and 1.5 M, and all mass transport properties were found to vary strongly with temperature. A superconcentrated electrolyte with LiTFSI in ACN was also fully characterized at 25 °C, and was found to have very different properties and interactions compared to LiPF6  in EC:DEC. The benefit of using the benchmarking method termed electrolyte masstransport resistivity (EMTR) compared to using only ionic conductivity was illustrated for several systems, including organic liquids, ionic liquids, solid polymers, gelled polymers, and electrolytes containing flame-retardant additives. TPP, a flame-retardant electrolyte additive, was evaluated using a HEV load cycle and was found to be unsuitable for high-power applications such as HEVs. A large-format commercial battery cell with a thermal management system was characterized using both experiments and a coupled electrochemical and thermal model during a PHEV load cycle. Different thermal management strategies were evaluated using the model, but were found to have only minor effects since the limitations lie in the heat transfer of the jellyroll. / Temperatur är en av de viktigaste parametrarna gällande ett litiumjonbatteris prestanda, säkerhet och åldring och har länkats till de främsta barriärerna för en storskalig kommersiell framgång för elbilar. Syftet med den här avhandlingen är att belysa vikten av temperatureffekter, samt att bidra med ingenjörsverktyg att studera dessa. Masstransporten för elektrolyten LiPF6  i EC:DEC karakteriserades fullständigt i temperaturintervallet 10 till 40 °C för LiPF6-koncentrationer på 0.5 till 1.5 M. Alla masstransport-egenskaper fanns variera kraftigt med temperaturen. Den superkoncentrerade elektrolyten med LiTFSI i ACN karakteriserades även den fullständigt vid 25 °C. Dess egenskaper och interaktioner fanns vara väldigt annorlunda jämfört med LiPF6  i EC:DEC. Fördelen med att använda utvärderingsmetoden elektrolytmasstransportresistivitet (EMTR) jämfört med att endast mäta konduktivitet illustrerades för flertalet system, däribland organiska vätskor, jonvätskor, fasta polymerer, gellade polymerer, och elektrolyter med flamskyddsadditiv. Flamskyddsadditivet TPP utvärderades med en hybridbils-lastcykel och fanns vara olämplig för högeffektsapplikationer, som hybridbilar. Ett kommersiellt storformatsbatteri med ett temperatur-kontrollsystem karakteriserades med b.de experiment och en kopplad termisk och elektrokemisk modell under en lastcykel utvecklad för plug-inhybridbilar. Olika strategier för kontroll av temperaturen utvärderades, men fanns bara ha liten inverkan på batteriets temperatur då begränsningarna för värmetransport ligger i elektrodrullen, och inte i batteriets metalliska ytterhölje. / <p>QC 20150522</p> / Swedish Hybrid Vehicle Center

This study focuses on the design, fabrication, and characterization of deterministically engineered, three-dimensional architectures to be used as high-performance electrodes in energy storage applications. These high-surface-area architectures are created by the robotically-assisted sequential electrodeposition of structural and sacrificial layers in an alternating fashion, followed by the removal of the sacrificial layers. The primary goal of this study is the incorporation of these highly laminated architectures into the battery electrodes to improve their power density without compromising their energy density. MEMS technologies, as well as electrochemical techniques, are utilized for the realization of these high-power electrodes with precisely controlled characteristic dimensions. Diffusion-limited models are adopted for the determination of the optimum characteristic dimensions of the electrodes, including the surface area, the thickness of the active material film, and the distance between the adjacent layers of the multilayer structure. The contribution of the resultant structures to the power performance is first demonstrated by a proof-of-concept Zn-air microbattery which is based on a multilayer Ni backbone coated with a conformal Zn film serving as the anode. This primary battery system demonstrates superior performance to its thin-film counterpart in terms of the energy density at high discharge rates. Another demonstration involves secondary battery chemistries, including Ni(OH)2 and Li-ion systems, both of which exhibit significant cycling stability and remarkable power capability by delivering more than 50% of their capacities after ultra-fast charge rates of 60 C. Areal capacities as high as 5.1 mAh cm-2 are reported. This multilayer fabrication approach is also proven successful for realizing high-performance electrochemical capacitors. Ni(OH)2-based electrochemical capacitors feature a relatively high areal capacitance of 1319 mF cm-2 and an outstanding cycling stability with a 94% capacity retention after more than 1000 cycles. The improved power performance of the electrodes is realized by the simultaneous minimization of the internal resistances encountered during the transport of the ionic and electronic species at high charge and discharge rates. The high surface area provided by the highly laminated backbone structures enables an increased number of active sites for the redox reactions. The formation of a thin and conformal active material film on this high surface area structure renders a reduced ionic diffusion and electronic conduction path length, mitigating the power-limiting effect of the active materials with low conductivities. Also, the highly conductive backbone serving as a mechanically stable and electrochemically inert current collector features minimized transport resistance for the electrons. Finally, the highly scalable nature of the multilayer structures enables the realization of high-performance electrodes for a wide range of applications from autonomous microsystems to macroscale portable electronic devices.

Le développement des véhicules électriques est actuellement en plein essor. Par contre, l’utilisation de ces véhicules est encore limitée en grande partie dû aux problèmes associés à la batterie : coût élevé, faible autonomie, long temps de recharge et durée de vie incertaine. L’influence de la température d’opération sur ces aspects de la batterie est grande et doit être considérée dès les phases initiales de conception de ce type de véhicule. Ce projet présente donc un modèle transitoire du système de gestion thermique d’un véhicule récréatif rechargeable. L’objectif de ce modèle est d’évaluer différentes options et configurations du système de refroidissement afin de minimiser l’impact de la température sur les performances du véhicule.

Avec l’arrivée en masse des véhicules à traction électrique, la puissance sollicitée à des blocs de cellules chimiques ne cesse d’augmenter. Les nouvelles technologies développées pour répondre à la demande exposent un nouveau problème jamais observé sur les assemblages multi-cellules : la disparité des paramètres internes. Une étude a démontré que ces faibles variations de capacité ou de résistance interne causeront une dégradation prématurée si elles ne sont pas prises en comptes. La littérature sur le sujet comprend plusieurs travaux qui tentent de palier à ce problème cependant très peu d’information n’est disponible pour quantifier ces divergences de paramètres internes. Ceux qui proposent des solutions viables le font généralement dans un contexte non transférable aux véhicules électriques ou hybrides. Ce document présente une étude complète de l’état de l’art sur l’utilisation et la gestion des batteries au lithium-ion ainsi que l’analyse d’un nouvel outil de mesure pour système de gestion de batteries permettant de mesurer et d’utiliser ces dispersions de paramètres internes des cellules. L’algorithme de mesure sera basé sur un système de classement des données recueillies novateur permettant de répertorié les données selon les conditions de conduites vécues lors de la mesure plutôt qu’en fonction du temps. La conception d’un système de gestion de batteries capable de mettre en œuvre cet outil de mesure dans un contexte de véhicule électrique ainsi que l’élaboration de partons de charge/décharge des cellules, afin de les plonger dans des conditions similaires à celles vécues par un bloc batterie de véhicule électrique, seront aussi exposées. La distribution des résistances internes des 16 cellules étudiées et une discussion de ces résultats complètera ce document.

The research presented in this thesis includes a detailed investigation into factors influencing ionic conductivity in the crystalline polymer electrolyte PEO₆:LiPF₆. It has previously been shown that preparing PEO₆:LiPF₆ with PEO modified with larger –OC₂H₅ end groups increases ionic conductivity by one order of magnitude [¹],primarily due to disruption of the crystal structure caused by the inclusion of the larger end groups. In this study it is shown that by reducing PEO molecular weight in crystalline PEO₆:LiPF₆ ionic conductivity is also increased. This was attributed to an increasing concentration of polymer chain end regions upon lowering molecular weight resulting in the creation of more defects, as well as possible increases in crystallite size resulting in longer continuous pathways for ion transport. Similar results were observed using both polydispersed and monodispersed PEO to prepare complexes. In addition, it is demonstrated here that ionic conductivity in crystalline polymerelectrolytes is not confined to PEO₆:LiXF₆ (X=P, As, Sb)[²][³] type materials. The structures and ionic conductivity data are reported for a series of new crystalline polymer complexes: the alkali metal electrolytes. They are composed of low molecular weight PEO and different alkali metal hexafluoro salts (Na⁺, K⁺ and Rb⁺), and include the best conductor poly(ethylene oxide)₈:NaAsF₆ discovered to date [⁴], with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)₆:LiAsF₆. A new class of solid ion conductor is reported: the crystalline small-molecule electrolytes. Such materials consist of lithium salts dissolved in low molecular weight glyme molecules [CH₃O(CH₂CH₂O)[subscript(n)]CH₃, n=1-12], forming crystalline complexes [⁵][⁶]. These materials are soft solids unlike ceramic electrolytes and unlike polymer electrolytes they are highly crystalline, are of low molecular weight and have no polydispersity. By varying the number of repeat units in the glyme molecule, many complexes may be prepared with a wide variety of structures. Here, ionic conductivity and cation transference number (t₊) data for several such complexes is presented [⁷][⁸][⁹].These complexes have appreciable ionic conductivities for crystalline complexes and their t₊ values vary markedly depending on the glyme molecule utilized. The differences in t₊ values can be directly attributed to differences in their crystal structures. [¹] Staunton, E., Andreev, Y.G. & Bruce, P.G. Factors influencing the conductivity of crystalline polymer electrolytes. Faraday Discussions 134, 143-156 (2007). [²] Gadjourova, Z., Andreev, Y.G., Tunstall, D.P. & Bruce, P.G. Ionic conductivity in crystalline polymer electrolytes. Nature 412, 6846 (2001). [³] Stoeva, Z., Martin-Litas, I., Staunton, I., Andreev, Y.G. & Bruce, B.G. Ionic Conductivity in the Crystalline Polymer Electrolytes PEO₆:LiXF₆, X = P, As, Sb. J. Am. Chem. Soc. 125, 4619-4626(2003). [⁴] Zhang, C., Gamble, S., Ainsworth, D., Slawin, A.M.Z., Andreev, Y.G. & Bruce, P.G. Alkali metal crystalline polymer electrolytes. Nature Materials 8, 580-584 (2009). [⁵] Henderson, W.A., Brooks, N.R., Brennessel, W.W. & Young Jr, V.G. Triglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (I). Chem. Mater. 15, 4679-4684 (2003). [⁶] Henderson, W.A., Brooks, N.R. & Young Jr, V.G. Tetraglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (II). Chem. Mater. 15, 4685-4690 (2003). [⁷] Zhang, C., Andreev, Y.G. & Bruce, P.G. Crystalline small-molecule electrolytes. Angewandte Chemie, International Edition 46, 2848-2850 (2007). [⁸] Zhang, C., Ainsworth, D., Andreev, Y.G. & Bruce, P.G. Ionic Conductivity in the Solid Glyme Complexes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 3,4). J. Am. Chem. Soc. 129, 8700- 8701 (2007). [⁹] Zhang, C., Lilley, S.J., Ainsworth, D., Staunton, E., Andreev, Y.G., Slawin, A.M.Z. & Bruce, P.G. Structure and Conductivity of Small-Molecule Electrolytes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 8-12). Chem. Mater. 20, 4039-4044 (2008).

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.

By replacing the intercalation electrode with a porous electrode and allowing lithium to react directly with O₂ from the air, the new rechargeable Li/O₂ battery system was studied. The porous cathode is comprised of carbon, catalyst and binder. The effect of every component was investigated. The catalyst was believed to play an important role in the performance of the electrode. A number of potential materials have been examined as the catalyst for the O₂ electrode. It suggests that the nature of the catalyst is a key factor controlling the performance of the O₂ electrode. Several catalysts based on first row transition metal oxides each with three different morphologies, bulk, nanoparticulate and mesoporous were studied. The influence of the morphology on the discharge and charge voltage, discharge capacity and cyclability were examined. Among all the catalysts studied, α-MnO₂ nanowires was found to be the best candidate. The reversible capacities of 3000 mAhg⁻¹(normalised by the mass of carbon) or 505 mAhg⁻¹ (based on the total mass of cathode + O₂ ) was obtained. Some of other factors, such as type of carbon, type of binder, type of electrolyte, the construction of cathode and the modification of the catalyst were also investigated, even just in the early stage. Capacity fading during cycling is the main problem in all the cases. A number of experiments were carried out to understand and attempt to avoid the fading problem. After successful synthesis of mesoporous α-Fe₂O₃ with unique properties (by Jiao et al.), the application of these materials in conventional Li battery was studied. Mesoporous α-Fe₂O₃ with ordered walls, mesoporous α-Fe₂O₃ with disordered walls and Fe₂O₃ nanoparticles were examined. It was also applied to examine the different factors that influence the rate of conversion electrodes, i.e., Li⁺ and e⁻ transport to and within the particles, as well as the rate of the two-phase reaction, demonstrating that for this conversion reaction electron transport to and within the particles is paramount.

Lithium-ion batteries with higher capacity and longer cycle life than that available today are required as secondary energy sources for a wide range of emerging applications. In particular, the cycling performance of several candidate materials for lithium-ion battery electrodes is insufficient because of the fast capacity fading and short cycle life, which is mainly a result of mechanical degradation. This dissertation mainly focuses on the issue of mechanical degradation in advanced lithium-ion battery electrodes. Thin films of tin electrodes were studied where we observed whisker growth as a result of electrochemical cycling. These whiskers bring safety concerns because they may penetrate through the separator, and cause short-circuit of the electrochemical cells. Cracking patterns generated in amorphous silicon thin film electrodes because of electrochemical cycling were observed and analyzed. A two-dimensional spring-block model was proposed to successfully simulate the observed cracking patterns. With semi-quantitative study of the cracking pattern features, two strategies to void cracking in thin-film electrodes were proposed, namely reducing the film thickness and patterning the thin-film electrodes. We also investigated electrodes consisting of low melting point elements and showed that cracks can be self-healed by the solid-to-liquid phase transformation upon cycling. Using gallium as an example, mechanical degradation as a failure mechanism for lithium-ion battery electrodes can be eliminated. In order to quantitatively understand the effect of surface modification on electrodes, we analyzed diffusion equations with boundary conditions of finite interfacial reactions, and proposed a modified potentialstatic intermittent titration technique (PITT) as an electro-analytical technique to study diffusion and interfacial kinetics. The modified PITT has been extended to thin-film geometry and spherical geometry, and thus can be used to study thin-film and composite electrodes consisting of particles as active materials.

The focus of this dissertation is to utilize chemical functionalization as a probe to investigate the reactivity of N-doped multiwalled carbon nanotubes (N-MWCNTs). The surface of N-MWCNTs, being a set of potentially reactive graphene edges, provides a large number of reactive sites for chemical modification, so considerable changes in chemical and physical properties can be envisaged. We observed that both reduction (dissolving metal reduction/alkylation) and oxidation (H2SO4/HNO3 and H2SO4/KMnO4 mixtures) of N-MWCNTs lead to formation of interesting spiral channels and spiraled carbon nanoribbons. A variety of techniques, including TGA, SEM, TEM, XRD and surface area measurements were used to analyze these new textural changes. We have developed methods to demonstrate that specific chemistry has occurred on these new structures. To this end, we introduced metal-binding ligands that could be used as probes in imaging and spectroscopic techniques including TEM, STEM, EDX, and EELS. A proposal for the underlying structure of N-MWCNTs responsible for the formation of the new textures is presented. We have investigated the performance of our materials as potential negative electrodes for rechargeable lithium ion batteries.

Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects. This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation and Billups reductive alkylation were used to functionalize N-CNOs to improve their dispersion properties in aqueous and organic solvents. Functionalized N-CNOs were characterized using various techniques such as TGA, TG-MS, Raman spectroscopy and pH-titrimetry. We designed an experimental method to isolate polycyclic aromatic adsorbates formed on the surface of oleum oxidized N-CNOs (ON-CNOs) and characterized them. A-CNOs, on the other hand are bigger than N-CNOs with diameters ranging from 20—40 nm. In this dissertation, we discuss the preparation of graphene structures by unzipping of A-CNOs using KMnO4 as oxidizing agent. These graphene structures were characterized using powder X-ray diffraction, TGA, BET nitrogen adsorption/desorption studies and compressed powder conductivity. This dissertation also focuses on lithiation/delithiation studies of N-CNOs, A- CNOs and A-CNO-derived graphene structures to use them as negative electrode materials in lithium-ion batteries. The cycling performances of these materials at a charge/discharge rate of C/10 were discussed. The cycling performance of N-CNOs was tested at faster charge/discharge rate of C.