During lithium-ion battery electrode fabrication, slurry drying conditions influence the resulting microstructure of electrodes. It has been found that the drying conditions can result in non-uniform cathode microstructures and material distributions. Accelerated drying, for example, is widely assumed to cause the binder in an electrode to migrate within the slurry, which can contribute to adhesion failure, and ultimately capacity fade and reduced battery life. While there are some conflicting studies regarding the aspects of accelerated drying that cause binder migration, there is not a widely used standard metric for measuring the gradient of binder across the thickness of an electrode. In this work, the vertical heterogeneity of electrodes, as measured using energy-dispersive X-ray spectroscopy (EDX), is correlated with different drying methods and rates. An improved metric for measuring the binder gradient in electrodes is proposed. For the electrodes in this study, binder migration is minimally affected by the drying method and the normalized binder gradient does not increase with increased drying rate. The results are compared to a drying physics model, and it is shown that further development of current models that predict binder gradient as a function of drying rate will need to be modified to more fully capture the physics of slurry drying.

This thesis focuses on the development of oxidatively stable cathode and electrolyte materials for sodium-based battery systems. This is primarily achieved through the use of solid-state nuclear magnetic resonance (ssNMR) and pulsed-field gradient (PFG) NMR spectroscopy. ssNMR is used to diagnose the primarily failure mode of the NaOB. It is found through a combined 23Na and 19F study that the main discharge product of the cell, NaO2, oxidizes both the carbon and polyvinylidene fluoride (PVDF) binder of the cathode to produce parasitic Na2CO3 and NaF. In a subsequent study, Ti4O7-coated carbon paper cathodes are implemented in an attempt to stabilize NaO2. The 23Na triple quantum magic angle spinning (3QMAS) and 1H to 23Na dipolar heteronuclear multiple quantum correlation (23Na{1H} D-HMQC) experiments are used to diagnose the failure modes of carbon-coated, and Ti4O7-coated cathodes. It is found that electrochemically formed NaO2 is significantly more stable in Ti4O7-coated cathodes, leading to longer lifetime NaOBs. Oxidatively stable electrolyte materials are also examined. Lithium and sodium bis(trifluoromethansulfonyl)imide (TFSI) in adiponitrile (ADN) electrolytes exhibit extreme oxidative resistance, but are unusable in modern cells due to Al corrosion by TFSI, and spontaneous ADN degradation by Li and Na metal. PFG NMR is used to investigate the transport properties of LiTFSI in ADN as a function of LiTFSI concentration. By measuring the diffusion coefficient of Li+ and TFSI as a function of diffusion time (Δ), diffusional behaviour is encoded as a function of length scale to study the short- and long-range solution structure of the electrolyte. It is found that at high concentrations, LiTFSI in ADN transports Li+ primarily through an ion-hopping mechanism, in contrast to the typical vehicular mechanism observed at low concentrations. This suggests significant structural changes in solution at high concentrations. The NaTFSI in ADN analogue is examined for its electrochemical properties in Na-ion and Na-O2 batteries. It is found that the oxidative resistance of ADN to Na metal is significantly increased at high concentrations, leading to reversible Na deposition and dissolution in cyclic voltammetry (CV) experiments. Linear sweep voltammetry (LSV) and chronoamperometry (CA) experiments on Al current collectors show that Al corrosion by TFSI is similarly suppressed at high concentration. This culminates in high concentration NaTFSI in ADN being able to reversibly intercalate Na3V2(PO4)2F3 (NVPF) cathodes in SIB half-cells for multiple cycles. The knowledge gained from exploring oxidatively stable cathode and electrolyte materials can be used in tandem for the development of a longer lifetime, more oxidatively stable, NaOB in the future. / Thesis / Doctor of Philosophy (PhD) / The continued development of rechargeable batteries is paramount in reducing the world’s reliance on fossil fuels, as they allow for the storage of electrical energy produced by renewable sources. This work primarily examines sodium-based batteries systems, such as the sodium-oxygen battery (NaOB) and sodium-ion battery (SIB), which are possible alternatives to the currently used lithium-ion battery (LIB) system. In order to produce energy, NaOBs produce sodium superoxide (NaO2) during the discharge process, which is formed on the carbon cathode. However, NaO2 is inherently unstable to carbon materials, causing degradation of the battery overtime. Ti4O7 is investigated as a stable coating material in NaOBs, used to coat the carbon cathode to make the system more stable to NaO2 degradation. The degradation processes in NaOBs are characterized by solid state nuclear magnetic resonance (ssNMR) spectroscopy, which uses strong superconducting magnets to probe the magnetic properties of, and consequently identify, the chemical species formed within the battery. It is found that the addition of the Ti4O7 coating inhibits NaO2 degradation, producing longer lifetime NaOBs. Subsequently, both Li-bis(trifluoromethansulfonyl)imide (LiTFSI), and NaTFSI, in adiponitrile (ADN) electrolytes are examined for their use in LIBs and SIBs, respectively. Electrolytes facilitate stable ion transport within the cell, and ADN electrolytes specifically allow for the use of higher voltage cathode materials, which can result in a higher energy density battery. The transport properties of LiTFSI in ADN electrolytes are studied by a pulsed-field gradient (PFG) NMR technique, that allows for the measurement of the rate of ion transport in the electrolyte. It is found that the mechanism of ion transport significantly depends on electrolyte concentration, which suggests significant changes to the electrolyte solution structure at high concentration. The electrochemical ramifications of this are studied for the NaTFSI in ADN electrolyte in SIBs. It is found that the electrolyte becomes substantially more stable at high concentrations, leading to more favourable charging and discharging behaviours when tested in SIBs. The work presented in this thesis illustrates the development of more stable, longer lifetime, batteries over a number of cell chemistries, using a variety of NMR and electrochemical characterization techniques.

Recently, lithium-ion batteries (LIBs) have achieved wide acceptance for various energy storage applications, such as electric vehicles (EVs) and smart grids. As a vital component in EVs, the performance of lithium-ion batteries in the last few decades has made significant progress. The development of a robust battery management system (BMS) has become a necessity to ensure the reliability and safety of battery packs. In addition, state of charge (SOC) estimation and thermal models with high-fidelity are essential to ensure efficient BMS performance. The SOC of a LIB is an essential factor that should be reported to the vehicle’s electronic control unit and the driver. Inaccurate reported SOC impacts the reliability and safety of the lithium-ion battery packs (LIBP) and the vehicle. Different algorithms are used to estimate the SOC of a LIBP, including measurement-based, adaptive filters and observers, and data-driven; however, there is a gap in feasibility studies of running these algorithms for multi-cell LIBP on BMS microprocessors. On the other hand, temperature sensors are utilized to monitor the temperature of the cells in LIBPs. Using a temperature sensor for every cell is often impractical due to cost and wiring complexity. Robust temperature estimation models can replace physical sensors and help the fault detection algorithms by providing a redundant monitoring system. In this thesis, an accurate SOC estimation and thermal modeling for lithium-ion batteries (LIBs) are presented using deep neural networks (DNNs). Firstly, two DNN-based SOC estimation algorithms, including a feedforward neural network (FNN) enhanced with external filters and a recurrent neural network with a long short-term memory layer (LSTM), are developed and benchmarked versus an extended Kalman filter (EKF) and EKF with recursive least squares filter (EKF-RLS) SOC estimation algorithms. The execution time of EKF, EKF-RLS, FNN, and LSTM SOC estimation algorithms with similar accuracy was found to be 0.24 ms, 0.25 ms, 0.14 ms, and 0.71 ms, respectively. The DNN SOC estimation algorithms were also demonstrated to have lower RAM use than the EKFs, with less than 1 kB RAM required to run one estimator. The proposed FNN and LSTM models are also used to predict the surface temperature of different lithium-ion cells. These DNN models are shown to be capable of estimating temperature with less than 2 ⁰C root mean square error for challenging low ambient temperature drive cycles and just 0.3 ⁰C for 4C rate fast charging conditions. In addition, a DNN model which is trained to estimate the temperature of a new battery cell, is found to still have a very low error of just 0.8 ⁰C when tested on an aged cell. Finally, an integrated physics, and neural network-based battery pack thermal model (LP+FNN) is developed and used to detect and identify different thermal faults of a LIBP. The proposed fault detection and identification method is validated using various thermal faults, including fan system failure, airflow lower and higher than setpoint, airflow blockage of submodule and temperature sensor reading faults. The proposed method is able to detect different cooling system faults within 10 to 35 minutes after fault occurrence. In addition, the proposed method demonstrated being capable of detecting temperature sensor reading offset and scale faults of ±3 ⁰C and ±0.15% or more, respectively with 100% accuracy. / Thesis / Doctor of Philosophy (PhD)

The research described here encompasses several different aspects of lithium ion battery operation including deep eutectic electrolytes, manganese trapping evaluation, silicon monoxide anodes, and in-situ NMR development under both static and spinning conditions. Individually, the results of these investigations as contained within the corresponding chapters contribute valuable insight. Collectively, they represent a snapshot into the numerous different ways in which nuclear magnetic resonance spectroscopy is applicable to lithium ion battery characterization. For instance, the deep eutectic electrolytes thus studied were amenable to diffusion coefficient characterization via the 1H, 7Li and 19F nuclei. This provided dynamical information on the anion, cation and neutral component and lent itself well towards parameterization of molecular dynamics simulations. The results thus obtained were useful in describing this relatively understudied class of electrolytes. Another example is that of the evaluation of manganese trapping. In this context 7Li NMR measurements were used to investigate the competitive inhibition of manganese trapping in crown ethers by lithium. Candidate crown ethers were thus evaluated for their ability to trap Mn2+ and Mn3+ in a lithium rich environment. Given the detrimental effects that manganese dissolution from cathode materials has on cycle life performance, the NMR enabled assessment of the appropriate chelating agents had identifiable importance. Additionally described was the progress made with silicon monoxide anodes supported on cellulosic substrates. The high active material loadings achieved, while also intriguing from a performance perspective, enabled 29Si MAS-NMR and 7Li static in-situ NMR measurements. For the in-situ measurements in particular, a novel cell design was constructed to utilize the advantages of a cellulosic substrate in this context. This has also enabled preliminary work on a spinning in-situ design. / Thesis / Doctor of Philosophy (PhD)

Li-ion batteries have enabled the widespread adoption of portable electronics and are becoming the technology of choice for electric vehicles and grid storage. One of the most promising ways to accommodate this demand is to increase the energy density and cycle life of battery electrode materials. Key strategies promoted in the literature include the use of nickel-rich cathodes as well as high-capacity anodes like silicon and lithium metal. While these materials enable a high energy density, this advantage is often counterbalanced with deficits such as poor stability and high cost. Multicomponent electrodes refer to strategies that try to leverage the relative advantages of different materials to offer an attractive compromise of energy density, cost, and cycle life. This thesis has investigated various aspects of multicomponent electrodes with a special emphasis on silicon-based anodes and high-entropy materials. Silicon (Si) is the second-most abundant element on earth and has one of the highest gravimetric capacities. However, silicon anodes are notorious for their poor cycle stability. Herein, improvements in the stability of silicon-based electrodes are achieved with multicomponent composite strategies involving the use of nanostructured spherical silicon. The nanosilicon is studied in high-fraction (80 wt% Si) and low-fraction (≤20 wt% Si) formulations to investigate both failure mechanisms and practical capacity retention, respectively. Composite strategies in which nanosilicon is encapsulated within a Li₄Ti₅O₁₂ ceramic or MOF-derived carbon matrix are shown to deliver superior capacity retention compared to simple composites of silicon and graphite. Considerable attention is given to the selection of a water-soluble binder and its role in electrochemical stability and electrode cohesion in high-loading silicon electrodes. It is found that unmodified high-molecular-weight sodium carboxymethyl cellulose offers better capacity retention compared to xanthan gum or low-molecular-weight binders. The high-entropy design strategy has created a diverse and largely unexplored set of multicomponent oxides and alloys with great potential as electrode materials. This strategy is applied to the family of layered cathodes, where the synthesis and electrochemical properties of the best-performing Li(NiCoMnTiFe)₁O₂ are reported. Despite the low Ni content, the cathode delivers a high initial capacity with unique overlithiation stability despite being charged to 4.4 V. Throughout the thesis, Operando XRD is used to reveal important insight into the lithiation mechanisms of the multicomponent electrodes including intercalation-based graphite, alloying-based silicon, and a novel organic azaacene.

<p dir="ltr">The thesis goal was to design a quasi-solid-state battery electrolyte, which was optimized to function at ambient as well as low temperatures. In the first project, an array of quasi-solid-state electrolytes were developed and compared. A series of electrochemical, spectroscopic, and thermal experiments in addition to imaging techniques determined a top performer as well as elucidated possible mechanistic explanations. This systematic study attempted to validate literature conclusions about the failure mechanisms governing batteries (solid-state batteries) at ultralow temperatures, while also offering hypothesis driven additional insight. The optimized electrolyte, which will be deemed as CSPE@2MMeTHF, performed well for several key reasons, traced to the co-solvent used (Me-THF), the salt concentration, and its formation of a stable and suitable cathode-electrolyte interphase. It was able to perform well at 25 °C, and down to -25 °C. The second part of the work, focused on further optimizing the electrolyte by removing a ‘polymer wetting/soaking’ step, removing a ceramic component, and pairing it with a recently discovered anodic electrode material. Given that narrowing the research gap for low temperatures requires both electrolyte and electrode design, it was important to consider this aspect of the problem as well. The cathodic electrode used for the first project, traditionally performs poorly at low temperatures, allowing for a suitable experimental control for the electrolyte. However, the new anodic electrode had two ways of storing lithium ions, as opposed to just one in the former, making it an attractive option for the stated goal of a low-temperature solid-state battery. This second project is akin to a ‘proof-of-concept’ work and there is much more room for further study, especially in preparing a full cell with the aforementioned electrodes cathode (LFP) and anode (NbWO) with the second SPE@51DMMeT electrolyte. In summary, this thesis shows method design to prepare solid-state electrolytes with portion of liquid, two successfully developed electrolyte systems for low temperatures, and a rigorous discussion of factors that affect electrochemical performance. Demonstrated research activities are of great value to defense as the current lithium-ion batteries does not perform well at subzero temperatures.</p>

With the increasing usage of electronics powered by lithium ion batteries, it is more and more importantto improve the recycling process. The current study is focused on reducing graphite content of disposedlithium batteries to aid the further treatment of the batteries. In larger picture, an increase of efficiencyleads to a less cost and less loss of material in recycling process. The approach used is to reduce graphitecontent by the agglomerated flotation, using the natural hydrophobicity of graphite. This approach candecrease the percentage of this mineral in the further recycling process of LIBs where the actual focus arethe valuable metals as lithium, cobalt, nickel and manganese. The results and conditions of flotation arecompared in cases where flotation feed material is the bulk material or thermally treated one.

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第24149号 / 人博第1052号 / 新制||人||246(附属図書館) / 2022||人博||1052(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 吉田 鉄平, 准教授 松井 敏明, 教授 林 晃敏 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

As the climate issue has affected most vehicle manufacturers, the number of electric cars in the world has increased in recent years. Scania's goal is that by 2030, 50 % of all their trucks sold in Europe will be powered by electricity. There are currently legal requirements for how transportation of batteries by road is allowed, depending on if the batteries are damaged, defective or prototype batteries. Scania currently has a method to transport these batteries. The working method consists of a safety box that is filled with the packing material Pyrobubbles in which the batteries are placed. However, Scania wants a better understanding of the function of Pyrobubbles, the safety box and its advantages and disadvantages, as well as whether there are better solutions. The work therefore intends to sort out these issues. In addition to reviewing the thermal properties of the materials, the work has been carried out from a SHE perspective on Scania’s request. This means that safety, health and the environment are taken into account. A literature study was conducted to investigate which alternative packaging materials were available as option to Pyrobubbles, as well as other manufacturers that are available for the safety box. Seven different packaging materials have been examined in the report, these are; absol, sorbix, vermiculite, sand, Pyrobubbles, glass- and stone wool. Two experimental studies were performed to investigate the properties of packing materials. All materials were tested in the cone calorimeter as three different experimental setups; dry, damp and inside a rust protection bag. Two full-scale experiments were also carried out where Pyrobubbles and rockwool were tested as packing material. In addition, a bow tie was created regarding the handling of packing material and an investigation of the ergonomics was conducted. The rust protection bag that is currently used at Scania to facilitate the packaging of Pyrobubbles contributes to unwanted heat release. The lowest heat release and best insulation capacity were measured for the sand. However, the sand is unmanageable to work with as it has a high density and contains carcinogenic particles. Rockwool is considered a good alternative to Pyrobubbles, which partly facilitates the work situation for employees and is also more accessible than Pyrobubbles. In order for rockwool to be accepted as a packing material, a certification of packing material and safety box must be done together, which applies to all new solutions. Keywords: Pyrobubbles, Lithium-ion battery, battery safety, ADR-S

Knowledge of battery health is very important. It provides insight into the capacity of a given system and allows the operators to plan ahead more efficiently. But measuring state of health (SoH) of a battery is difficult, and takes time. More importantly, the battery needs to be taken out of operation to be analysed correctly. This paper aims to evaluate a proposed linear regression method for predicting battery health, based on easily acquired operational data. The main predictor being voltage deviation, a characteristic of battery voltages during charge/discharge cycles. Using this method, the only time a battery would need to be extracted is to gather training data. Then, the model could be used for similar batteries to predict their SoH. Meaning those systems would never need to be halted, increasing productivity. The results of this paper is that the data used was not suitable for linear regression. There were problems with heteroskedasticity and non-normality of the residuals, but mainly the estimated parameter for the relationship between voltage deviation and SoH ran contrary to established theory. Which could not be overlooked. Therefore, the estimated models should not be used to predict SoH. To accomplish the goal of accurate SoH prediction, more research should be conducted and a better sample used.