The applications of Li-ion batteries in the electronics and vehicle industry is increasing at a very rapid pace. This is primarily due to superior properties such as high specific energy storage and power as well as wider operation temperature ranges. Additional potential for improved properties is connected to capacity losses with time and the thereby resulting limitations of lifetime of batteries. The lifetime of a battery is strongly related to the mechanical and chemical degradation of the active material of electrodes during repeated electrochemical reactions at charging and discharging. To identify this phenomenon from a mechanical perspective, the mechanical properties of the electrode active layers should be characterized. Additionally, with the aid of mechanical properties, realistic electro-chemo-mechanical models should be developed to comprehend the mechanisms causing capacity fade. In the first part of this thesis, macroscopic material properties of the active layers of Li-ion battery electrodes were measured with a unique bending test technique. Contrary to methods previously used; it is capable to overcome the challenges that were encountered in other traditional testing techniques. In papers 1 and 2 this bending test technique (U-shaped bending test), is used to characterize the elastic and viscoelastic behavior of NMC cathodic and graphite anodic active layers, respectively. By using single-sided thin electrode specimens in U-shape bending tests, it was possible to distinguish tensile and compressive elastic and viscoelastic behavior of the electrode active materials. The tensile Young’s moduli of cathodic and anodic active layers are found as 0.73 GPa and 1 GPa, respectively. On the other hand, the compressive Young’s moduli show a stiffening behavior at increasing strains. Stiffnesses between 1.3 GPa and 2.8 GPa for the cathodic active layer, and between 1 GPa and 3.8 GPa for the anodic active layer were recorded. This compressive behavior of the electrode active layers is expected as a result of the porous nature of the materials. In addition, the viscoelastic behavior of the electrode active layers is expressed through Prony series. It was observed that the behavior can be described by a short term (minutes) and a long term (hours, days) relaxation. In paper 3, a statistical representative volume element is introduced to predict the elastic properties of a dry cathodic electrode active layer. A porous cathodic electrode active layer that is composed of NMC active particles and polymeric binder material with conductive carbon additives is modeled as a face-centered-cubic structure. Several particle-binder and particle-particle interaction conditions are repeated 50 times with random orientations. Based on the statistics for each interaction case, Young’s modulus is estimated. The results show a good agreement with the experimental findings from Paper 1. Furthermore, particle-particle and particle-binder contact force distributions are calculated for 3% of particle swelling. The characteristics of the force distributions are correlated with the typical material failures in the active layer such as particle cracking and binder debonding. The statistical data obtained here are also used to improve an analytical model that was previously derived to estimate the elastic properties of active porous layers. The analytical model, complemented by the statistical results, showed an excellent agreement with the finite element simulations. / <p>QC 230124</p>

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This work presents novel modeling and experimental techniques that provide insight into liquid-phase mass transport and electron transfer processes in lithium-ion batteries. These included liquid-phase ionic mass transport (conduction and diffusion), lithium diffuion in the solid phase and electronic transport in the solid phase. Fundamental understanding of these processes is necessary to efficiently design and optimize lithium-ion batteries for different applications. To understand the effect of electrode structure on the electronic resistance of the cathode, we tested power performance of cathodes with combinations of three different carbon conductivity additives: vapor-grown carbon fibers (CF), carbon black (CB) and graphite (GR). With all other factors held constant, cathodes with a mixture of CF+CB were found to have the best power-performance, followed by cells containing CF only and then by CB+GR. Thus, the use of carbon fibers as conductive additive was found to improve the power performance of cells compared to the baseline (CB+GR). The enhanced electrode performance due to the fibers also allows an increase in energy density while still meeting power goals. About one-third of the available energy was lost to irreversible processes when cells were pulse-charged or discharged at the maximum rate allowed by voltage-cutoff constraints. We developed modeling and experimental techniques to quantify tortuosity in electrolyte-filled porous battery structures (separator and active-material film). Tortuosities of separators were measured by two methods, AC impedance and polarization-interrupt, which produced consistent results. The polarization-interrupt experiment was used similarly to measure effective electrolyte transport in porous films of cathode materials, particularly films containing lithium iron phosphate. An empirical relationship between porosity and the tortuosity of the porous structures was developed. Our results demonstrate that the tortuosity-dependent mass transport resistance in porous separators and electrodes is significantly higher than that predicted by the oft-used Bruggeman relationship. To understand the dominant resistances in a lithium battery, we developed and validated a model for lithium iron phosphate cathode. In doing so we considered unique physical features of this active material. Our model is unusual in terms of the range of experimental conditions for which it is validated. Various submodel and experimental techniques were used to find physically realistic parameters. The model was tested with different discharge rates and thicknesses of cathodes, in all cases showing good agreement, which suggests that the model takes into account physical realities with different thicknesses. The model was then used to find the dominant resistance for the tested cathodes. The model suggests that the inter-particle contact resistance between carbon and the active-material particles was a dominant resistance for the tested cathodes.

As the cost of variable renewable energy resources like wind and solar decline rapidly the major barrier to decarbonization of the electrical grid becomes that of energy storage. Current storage technologies are much too expensive to justify widespread adoption and it is unclear what type of technology is even capable of fulfilling this role. Flow batteries are an often proposed technological solution to this problem but they are plagued by high cost and reliability issues due to the expensive and complex balance of plant included in the system design. In this work a new design for a gravity driven flow battery is explored which is capable of drastically lowering the cost of flow batteries by removing the pumps and membranes and replacing their function with density stratification and flow driven by the density change of the electrode reactions. A design for a zinc-bromine battery which makes use of this free convection during operation is explored. The system is studied through construction of prototype cells, exploration of key design variables, and a techno-economic analysis of the technology is performed showing cost viability. The free convection phenomenon which underlies the battery operation is expanded upon by connecting non-dimensional correlations in heat transfer with electrochemical transport equations in order to create predictive understanding of flow behavior based on system composition. This correlative understanding is used to construct a model of a zinc-bromine gravity driven flow battery. This model shows results which align with experimental data and gives insight into the complex transport dynamics of the system.

The pursuit of reliable and high-performance batteries has fueled extensive research into new battery chemistries and materials, aiming to enhance the current lithium-ion battery technologies in terms of energy density and safety. Among the potential advancements, solid-state batteries (SSBs) have captured significant attention as the next-generation energy storage technology. One key factor contributing to their appeal is the utilization of solid-state electrolytes (SSEs) with a wide electrochemical stability window (ESW), making SSBs compatible with high-voltage cathodes. The energy density of SSBs can be further improved by employing the “holy-grail” anode, Li-metal, which boasts the lowest working voltage (-3.04 V vs. Li+/Li) and an ultrahigh theoretical capacity (3860 mAh g−1). Consequently, these batteries are referred to as lithium metal batteries (LMBs). However, realizing the full potential of LMBs presents formidable challenge, including the low ionic conductivity of current SSEs, large interfacial resistance between SSE and electrodes, uncontrollable interfacial reactions, and the growth of Li dendrites.  Typically, SSEs can be categorized into three types. Among these, solid composite electrolytes (SCEs) are considered the most promising choice for solid-state LMBs due to their combination of high ionic conductivity and excellent mechanical strength from inorganic solid electrolytes (ISEs) and the flexibility and good interface compatibility provided by solid polymer electrolytes (SPEs). Polymeric ionic liquids (PolyILs), which contain both ionic liquid-like moieties and polymer frameworks, have emerged as highly attractive alternatives to traditional polymers in SCEs.  The overall objective of this thesis was to develop PolyIL-based SCEs with enhanced ionic conductivity, wide ESW, high Li+ transference number, and reduced electrodes/electrolyte interface resistance. The main progress achieved in this thesis is as follows: 1. We selected three F-based Li-salts to prepare SPEs using poly(ethylene oxide) and polyimide. The investigation focused on assessing the impact of molecular size, F content, and chemical structures (F-connecting bonds) of these Li-salts. Additionally, we aimed to uncover the formation process of LiF in the solid electrolyte interphase (SEI). The result revealed that the F-connecting bond plays a more significant role than the molecular size and F element content, resulting in slightly better cell performance using LiPFSI compared to LiTFSI and substantially better performance compared to LiFSI. The preferential breakage of bonds in LiPFSI was found to be related to its position to Li anode. Consequently, we proposed the LiPFSI reduction mechanism based on these findings. 2. Using the template method, we synthesized a monolayer SCE with enhanced Li+ transference number and high ionic conductivity. In this study, boron nitride (BN) nanosheets with a high specific surface area and richly porous structure were employed as inert inorganic filler. These BN nanosheets played a crucial role in homogenizing the Li+ flux and facilitating the Li+ transmission to suppress Li dendrite growth. When integrated into a LiFePO4//Li cell with the optimized SCE, the assembled battery demonstrated remarkable cycling performance.  3. A monolayer GSCE with multifunctionality was synthesized via a natural sedimentation and subsequent UV-curing polymerization technique. This innovative method capitalizes on intrinsic gravity, allowing for the integration of multiple functions within a single layer, thereby eliminating the additional interlayer resistance. The developed GSCE provides an optimum Li+ transportation path and enhanced Li+ transference number, leading to an enhanced ionic conductivity and a long cycle life of Li//Li cells and SSLMBs. Compared with the monolayer uniform SCEs, the gradient structure also alleviates the uncoordinated thermal expansion between fillers and PolyIL, avoiding increased stress during the cycle and battery capacity fade.

The global transition to renewable energy sources is placing high demands on the development of effective energy storage methods, the most prevalent being batteries. Dual-ion batteries are a new battery technology that takes advantage of the simultaneous intercalation of both cations and anions. Dual-ion batteries can be made from environmentally friendly materials such as organic compounds or conductive polymers that are made up of highly abundant elements. These often have a lower cell voltage than metal-based batteries, allowing water-based electrolytes to be used without decomposing. This master’s thesis presents the synthesis, and electrochemical testing of a nanofibrous polyaniline cathode. It also presents the synthesis and electrochemical testing of two anodes being and graphene-enhanced polyimide, and perylene tetracarboxylic diimide (PTCDI). Aqueous ammonium sulfate of 1 M or 3 M concentration is used as electrolyte. A novel full-cell dual-ion battery is also constructed using polyaniline and PTCDI as electrodes. The addition of graphene to polyimide results in changes in morphology with decreased pore size and increased surface area for supposed improved reaction kinetics with the electrolyte. The electrochemical testing of this anode is however not successful. The polyaniline cathode has an early charge/discharge capacity of 184.5/85.2 mAh/g that decreases to 40.4/45.8 mAh/g after 100 cycles. The PTCDI anode has an early charge/discharge capacity of 80.2/87.3 mAh/g but cannot be evaluated after a few cycles due to electrolyte decomposition. For this reason, the electrolyte dependence on ammonium sulfate concentration is also investigated. An increase in molarity from 1 M to 3 M leads to increased stability of the electrolyte. The polyaniline//PTCDI full-cell has a voltage of 1.2 V and shows an early charge/discharge capacity of 17.6/11.9 mAh/g that decreases to 9.1/7.2 mAh/g after 100 cycles where the efficiency stabilizes at 80%.

Electrochemical Energy Storage Systems are a viable and popular solution to fulfill energy storage requirements for energy generated through sustainable energy resources. With the increasing demand for Electrical Vehicles (EVs), Lithium-ion batteries (LIB) are being widely and getting popular compared to other battery technologies due to their energy storage capacity. However, LIBs suffer from disadvantages such as battery life and the degradation of electrode material with time, that can be improved by understanding these mechanisms using experimental and computational techniques. Further, it has been experimentally observed and numerically determined that lithium-ion intercalation induced stress and thermal loading can cause capacity fading and local fractures in the electrode materials. These fractures are one of the major degradation mechanisms in Lithium-ion batteries. With LixMn2O4 as a cathode material, stress values differ widely especially for intermediate State Of Charge (SOC), and very few attempts have been made to understand the stress distribution as a function of SOC at molecular level. Therefore, the estimates of mechanical properties such as Young’s modulus, diffusion coefficient etc. differ, especially for partially charged states. Further, the effect of temperature, particularly elevated temperatures, have not been taken into the consideration. Studying these parameters at the atomic scale can provide insight information and help in improving these materials lifetime. Hence, molecular/atomic level mathematical modelling has been used to understand capacity fade due to Lithium-ion intercalation/de-intercalation induced stress. Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) [1], that is widely used for atomic simulations, has been used for the simulation studies of this dissertation. Thus, the objective of this study is to understand the fracture mechanisms in the Lithium Manganese Oxide (LiMn2O4) electrode at the molecular level by studying mechanical properties of the material at different SOC values using the principles of molecular dynamics (MD). As part of the model validation, the lattice parameter and volume changes of LixMn2O4 as a function of SOC (0 < x < 1) has been studied and validated with respect to the experimental data. This validated model has been used for a parametric study involving the SOC value, strain-rate (charge and discharge rate), and temperature. Based on the validated MD setup, doping and co-doping studies have been undertaken to design and develop new and novel cathode materials with enhanced properties. In the absence of experimental data for the new engineered structures, validation with Quantum Mechanics generated lattice structures has been done. The results suggest that lattice constant values obtained from both MD and QM simulations are in good agreement (∼ 99%) with experimental values. Further, Single Particle Model (SPM) based macro scale Computational Fluid Dynamics findings show that co-doping has improved the material properties especially for Yttrium and Sulfur doped structures which can improve the cycle life anywhere between 600-7000 cycles. Further in order to reduce the required computational time to obtain minimum potential energy ionic configuration out of millions of scenario, Artificial Neural Network (ANN) technique is being used. It improved the processing time by more than 88%. / Thesis / Doctor of Philosophy (PhD)

The possibility of measuring the state of health of a NiMH battery without doing it in a lab is evaluated, the goal was to see if it was possible to perceive any differences between batteries of different states of health and whether it’s worth further exploring this solution in a more detailed manner. In order to try and extract and analyze the state of health of the batteries a series of tests consisting of discharging batteries at different lengths of times and different resistive loads were made, the voltage of the batteries being captured by a multimeter. The study shows that getting the state of health of a battery with simple components is a possibility and is useful for battery-powered items. Situations where batteries can’t deliver enough energy for the item to function can be prevented by measuring the health of the batteries and then subsequently switching out the batteries if needed.

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.

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.