Over the last century, almost all of the carbon materials developed for the energy industry are derived from fossil fuels. The growing global concerns about energy needs, fossil fuels consumption, and the related environmental issues have motived scientists to find new, green and sustainable energy resources such as the wind, solar and biomass energy. Essentially, biomass-derived materials can be utilized in energy storage and conversion devices such as Li-ion batteries, fuel cells, and supercapacitors. Among the biomass resources, lignin is a high volume byproduct from the pulp and paper industry and is currently burned to generate electricity and steam. The pulp and paper industry has been searching for high value-added uses of lignin to improve its overall process economics. The importance of manufacturing valuable materials from lignin is, discussed in Chapter 2, demonstrating the need for a facile, green and scalable approach to synthesize bio-char and porous carbon for use in Li-ion batteries. From this context, lignin is first carbonized in water at 300 °C and 103 bar to produce bio-char, which is then graphitized using a metal nitrate catalyst at 900-1100 °C in an inert gas at 1 bar. Graphitization effectiveness of three different catalysts, iron, cobalt and manganese nitrates was examined. The obtained materials were analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both annealing temperature and the catalyst affects the degree of graphitization. High-quality graphitization is obtained by using Mn(NO3)2 at 900 °C or Co(NO3)2 catalysts at 1100 °C. Research on various energy storage materials for supercapacitors has grown rapidly in the recent years. Various advanced materials have been shown as a promising candidate for future’s high-energy supercapacitor electrodes. For a material in a supercapacitor electrode to be considered, it must show promising results for its specific power and energy density, electrical conductivity, surface properties, durability, surface area and pore-size distribution in order to design and develop high-performance supercapacitor devices. The industrial applications of supercapacitors have not been satisfied due to the low energy density (the commercially available supercapacitors have between 5 to 10 times less energy density than that of batteries) and moderate charge-discharge rate of supercapacitor electrode. Thus, chapter 3 was aimed to design and synthesize nitrogen-doped carbon materials that show the characteristic of high-energy and high-power density supercapacitor electrodes with a long cycle life. With this aim, organosol lignin was successfully converted into N-doped carbon materials using a two-step conversion process. The nitrogen content in the carbon was up to 5.6 wt.%. The synthesize materials exhibit high surface area up to 2957 m2/g with micro/meso porosity and a sheet-like structure. The N-doped carbon produced at 850 oC exhibited a high capacitance value of 440 F g-1 at a 1 mV s-1 scan rate and demonstrated excellent cyclic stability over 30,000 cycles in 1 M KOH. In addition, the NC-850 delivers a high energy density of 15.3 W h kg-1 and power density of 55.1 W kg−1 at 1 mV s-1. Therefore, this study suggests that N-doped carbon materials synthesized from a pulp and paper byproduct, lignin, are promising environmentally-sustainable candidates for supercapacitor applications. Challenges for commercialization of fuel cells include high operation cost, inadequate operational stability, and poisoning by H2O2. To address the challenge, costly Pt-based catalysts are needed in order to facilitate the oxygen reduction reaction (ORR) at the cathode and the hydrogen oxidation reaction (HOR) at the anode. In chapter 4, alternative metal-free ORR catalyst materials derived from lignin are studied in order to simultaneously enhance the catalytic activity, lessen the Pt dependency and reduce the excessive costs associated. Calcium sulfonate lignin was successfully converted into sulfur self-doped carbons via in-situ hydrothermal carbonization and followed by post-annealing treatment. The sulfur content in the as-prepared porous carbons is up to 3.2 wt.%. The resulting materials displayed high surface areas (up to 660 m2 g-1) with micro/meso porosity and graphitic/amorphous carbon structure. The as-prepared sulfur self-doped electrode materials (SC-850) were tested as a potential cathodic material for ORR. The number of electrons transferred per molecule was measured to be ~ 3.4 at 0.8 V, which approaches the optimum 4 electron pathway. Additionally, S-doped materials were also applied as a supercapacitor electrode material. The SC-850 electrode exhibited a high specific and volumetric capacitance values of 225 F g-1 and 300 F cm-3 at a scan rate of 0.5 A g-1. The SC-850 electrode also exhibited consistent response over 10,000 cycles at harsh conditions. It was shown that the metal-free SC-850 is a promising electrode material for supercapacitors and ORR applications. All of the studies presented in this dissertation involve the development and application of carbon-based materials derived from lignin and its application towards the Li-ion batteries, supercapacitor, and fuel cell. Insight into the applicability of lignin-derived carbon materials towards electrochemical applications is made readily available, supplemented by detailed physical, chemical and electrochemical characterization, to examine the specific factors influencing the Li-ion batteries, supercapacitor, and electrocatalysis of fuel cell activity.

Ageing mechanisms of graphite/NMC Li-ion batteries have been studied using computational methods. The purpose of the project was to investigate solid electrolyte interphase (SEI) formation and growth during cycling of the battery. The SEI layer formation was considered to be a reason for capacity fade of the battery. Irreversible consumption of cyclable Li-ions and increased resistance in the layer was considered to be the result of solid electrolyte layer formation and these two effects were studied more closely using cell modelling. The battery cycled with three cases of fast charge rates (2C, 4C and 6C) and the same discharge rate (1C) showed a thick film formation on the anode side and a higher film resistance when compared to the battery cycled with the same charge/discharge rate (1C). All investigated batteries were affected by the studied ageing mechanism, and in the case of batteries cycled with fast charge rates, the ageing was even more pronounced. The report includes a general description of Li-ion battery functionality, a summary of ageing mechanisms and a mathematical description of the electrochemistry governing the battery and implemented in the software.

This work deals with electrolytes and ionic liquids for Li-ion batteries. Following interaction of electrolytes and ionic liquids to electrodes material. In the theoretical part attention is focused on the description of battery electrolytes and ionic liquids for lithium-ion batteries.

This work is focused on lithium-ion batteries in general and their modeling capabilities in ANSYS Fluent. The various advantages and disadvantages of li-ion batteries are describes in my work. There are also described the various models and submodels offered by ANSYS Fluent. An essential part of the work is to model the real battery and compare the results between the real battery and the simulation itself. Finally, simulation of battery breakdown is performed.

Performance degradation of lithium-ion batteries (LIBs) from in-service abuse was analyzed using novel dynamic abuse tests and sensor-based in-situ monitoring of battery state of health (SOH). The relation between dynamic impact and structure changes of LiCoO₂ (LCO) electrode was analyzed through a nano-impact test directly applied to the electrode and Raman imaging. After the electrode structure damage induced by the dynamic loading was analyzed, the performance of the LIBs with the abused electrodes was evaluated to establish the relation between the number of impact cycles and LIB performance degradation. The mechanism of impact related LIB capacity decrease was analyzed, and the capacity change can be predicted based on the impact abuse history using this approach. In order to provide more detailed information on the battery performance degradation caused by the in-service dynamic loads, a dynamic aging testing platform was designed to simulate in-service vibration and impact experienced by the LIBs. Based on the lessons learned, a sensor network was constructed to provide a comprehensive in-situ evaluation of the SOH of commercial batteries. Mechanisms of LIB capacity fade, temperature increase, and cell deformation from cycling in representative dynamic environments were analyzed and correlated with theoretical predictions. Difference between the aging of a battery pack and that of a single cell was also investigated, which presented the influence of current imbalance on the SOH decay of battery packs. SEM imaging, Raman imaging, and electrochemical impedance spectroscopy (EIS) analysis were also applied to support the sensor network measurements.<br><div> In order to provide an early detection of catastrophic LIB failure such as thermal runaway, an internal resistance temperature detector (RTD) based electrode temperature monitoring approach was developed. By embedding the RTD into LIBs with 3D printing technique, electrode temperature can be collected during ordinary cycling and electrical abuse of LIBs, such as external short circuit and overcharge. The internal RTD presented high measuring efficiency, while there was no interference between the sensor measurement and battery operation. The internal RTD detected the short circuit event and overcharge failure prior of time: the efficiency of the internal RTD was 6-10 times higher than the external RTD in the short circuit test. This provided the chance for early detection and prevention of catastrophic LIB failures. Besides, with the detailed information on electrode temperature evolution during LIB thermal runaway available, the internal RTD also provided the chance to enhance the understanding of the thermal runaway mechanism.</div>

Next-generation batteries with improved microstructure and performance are on their way to meet the market demands for high-energy and power storage systems. Among different types of batteries, Li-ion batteries remain the best choice for their high energy density and long lifetime. There is a constant but slow improvement in Li-ion batteries by developing new materials and fabrication techniques. However, further improvements are still needed to meet government and industry goals for cost, cycling performance, and cell lifetime. A fundamental understanding of particle-level interactions can shed light on designing new porous electrodes for high-performance batteries. This is a complex problem because electrodes have a multi-component, multi-phase microstructure made through multiple fabrication processes (i.e., mixing, coating, drying, and calendering). Each of these processes can affect the final microstructure (particle and pore locations) differently. This work seeks to understand the porous microstructure evolution of Li-ion electrodes during the drying and calendering fabrication processes by a combination of modeling and experimental approaches. The goal is to understand the mechanisms by which the electrode components and fabrication processes determine the battery microstructure and subsequent cell performance. A multi-phase smoothed particle (MPSP) model has been developed on a publically available simulation platform known as LAMMPS. This model was used to simulate particle-level interactions and predict the mechanical and transport properties of four fabricated electrodes (i.e. a graphite anode and three traditional metal oxide cathodes). One challenge was to include different electrode components and their interactions and relate them to physical properties like density and viscosity that can be measured experimentally. Another challenge was to generate required electrode property data for model validation, which in general was not found in the literature. Therefore, a series of experiments were conducted to provide that information, namely slurry viscosity, electronic conductivity, porosity, tortuosity, elastic modulus, and electrode crosssections. Understanding these properties has value to the battery community independent of their use in this study. The MPSP model helps us explain observed transport heterogeneity after calendering but brings up new questions about the drying process that have not been addressed in previous works. Therefore, the drying fabrication step was studied experimentally in more detail to fill this knowledge gap and explain our simulation results. The MPSP model can also be used as a predictive tool to explore the design space of Li-ion electrodes where conducting the actual experiments is very challenging. For example, the distinct effect of particle size, shape, orientation, and stiffness on electrode transport and mechanical properties are difficult to determine independently, and therefore this model is an ideal tool to understand the effect of these properties. The final model, which is publically available, could be used with adjustments by future workers to test new materials, fabrication processes, or electrode design (e.g., a multi-layered structure).

No description available.

The present poster contribution aims at optimization of electrochemical properties of titania (N doped anatase TiO2 / N) and Li-Ti ternary oxides (Li4Ti5O12, LTO) with respect to their performance as anode materials in Li-ion battery by using mechanochemical effects.

The present poster contribution aims at optimization of electrochemical properties of titania (N doped anatase TiO2 / N) and Li-Ti ternary oxides (Li4Ti5O12, LTO) with respect to their performance as anode materials in Li-ion battery by using mechanochemical effects.

Electrode microstructure directly affects ion and electron transport and, in turn, has a strong correlation to battery performance. Understanding the separate yet complementary effects of ionic and electronic transport in cell behavior is a challenge. This work provides through a combination of experiments and modeling a better understanding of the relationship between three aspects of the cell: ion transport within the electrode, electrode uniformity, and cell degradation. The first part of this work compares two experimental methods that determine ion transport in terms of tortuosity, a dimensionless geometric factor. The polarization-interrupt and blocking-electrolyte methods measure effective diffusivity and conductivity, respectively. The tortuosity of several commercial-quality electrodes was measured using both methods, producing reasonable agreement between the two methods in most cases. Next, the effect of cell cycling on ionic and electronic transport of electrodes was investigated. Using the blocking electrolyte method, the tortuosity of electrode films at varying extents of cycling was determined. Variations in electronic resistivity were quantified by micro-scale measurements using a previously developed micro-four-line probe. The changes in tortuosity and electronic resistivity were investigated for a graphite anode and several cathode chemistries including LiCoO2, LiNixCoyMnzO2, LiFePO4, and blends of transition metal oxides. Clear evidence of changes in tortuosity and electronic resistivity was observed during cell formation and cycling. The magnitude of the changes strongly depended on the chemistry of electrodes and cycling conditions. The results indicate that, under normal cycling conditions, electronic resistivity increases while tortuosity unexpectedly decreases. However, accelerated cycling conditions (i.e. elevated temperature) can lead to both electronic resistivity and tortuosity increase. Finally, the interplay of electrode tortuosity heterogeneity and Li-plating was investigated. The Li-plating reaction was incorporated into a Newman-type model and validated using the voltage profile and capacity-loss data from experiments. The simulation result shows that a heterogeneous anode can cause non-uniform Li plating while cathode heterogeneity did not have a significant effect. The Li-plating profile across the thickness of the anode with cell cycling showed that Li tends to plate at the high tortuosity region near the separator. Unexpectedly, Li plating tends to shift to the current collector side upon a sufficient increase in porosity close to the separator. Simulated capacity loss vs. cycling data indicates that there is a feedback mechanism with cycling: as cycling continues the rate of Li plating for the high-tortuosity region decreases at the separator side and the other two regions will eventually catch up in terms of plating.