MSc (Physics) / Department of Physics / Currently the dye sensitized solar cells have attracted more attention due to their low cost, transparency and flexibility. These types of solar cells use the dye molecule adsorbed on TiO2 semiconductor in Nano architecture with the role of absorbing photons, in recent research attempts are being made to shifts the absorption spectral of TiO2 to visible and near infrared–region of solar spectrum to achieve maximum photo absorption which yields to an increase in the efficiency of the dye sensitized solar cells. In the current study, density functional theory (DFT) was used to model two croconate dyes (CR1 and CR2), one with an electron donating methyl group (CR1) and the other with an electron –withdrawing caboxyl group (CR2). The geometric, electronic and optical properties of these dyes were compared. The adsorption behaviour of the two dyes on (010 and 100) anatase TiO2 surfaces were investigated in this study by employing first principle calculation based on DFT using a plane-wave pseudo potential method. The generalized gradient approximation (GGA) was used in the scheme of Perdew-Burke Ernzerhof to describe the exchange -correlation function as implemented in the CASTEP package in Material Studio of BIOVIA. The adsorption results shows a spontaneous electron injection followed by efficient regeneration of the oxidized dye molecules by the electrolyte and strong binding ability of CR2 to the TiO2 surface, but also shows a comparable binding strength of CR1. The results of this study will help in the design of high efficient dye for DSSCs. / NRF

Thesis (Ph.D. (Physics)) -- University of Limpopo, 2021 / Titanium dioxide is among the most abundant materials and it has many of interesting physical and chemical properties (i.e., low density, high thermal and mechanical strength, insensitivity to corrosion) that make it a compound of choice for electrodes materials in energy storage. There are, however, limitations on the theoretical side to using the main electronic structure theories such as Hartree-Fock (HF) or densityfunctional (DFT) especially for large periodic and molecular systems. The aim of the theses is to develop a new, widely transferable, self-consistent density functional tight binding SCC-DFTB data base of TiO2, which could be applied in energy storage anodes with a large number of atoms. The TiO2, LiTiO2 and NaTiO2 potentials were derived following the SCC-DFTB parameterization procedure; where the generalized gradient approximation (GGA) and local density approximation (LDA) exchange-correlation functional were employed yielding Slater-Koster DFTB parameters. The results of derived parameters were validated by being compared with those of the bulk rutile and brookite polymorphs. The structural lattice parameters and electronic properties, such as the bandgaps were well reproduced. Most mechanical properties were close to those in literature, except mainly for C33 which tended to be underestimated due to the choice of exchange-correlation functional. The variation of the bulk lattice parameter and volume with lithiation and sodiation were predicted and compared reasonably with those in literature. The newly derived DFTB parameters were further used to calculate bulk properties of the anatase, which is chemically more stable than other polymorphs. Generally, the accuracy of the lattice structural, electronic and mechanical properties of the bulk anantase were consistent with those of the rutile and brookite polymorphs. Furthermore, nanostructures consisting of a large number of atoms, which extend beyond the normal scope of the conventional DFT calculations, were modelled both structurally and electronically. Structural variations with lithiation was consistent with experimental and sodiation tends to enhance volume expansion than lithiation. Anatase TiO2 and LiTO2 nanotubes of various diameters were generated using NanoWrap builder within MedeA® software. Its outstanding resistance to expansion during lithium insertion and larger surface area make the TiO2 nanotube a promising candidate for rechargeable lithium ion batteries. The outcomes of this study will be beneficial to future development of TiO2 nanotube and other nanostructures. Lastly, our DFTB Slater-Koster potentials were applied to recently discovered trigonal bipyramid (TB), i.e. TiO2 (TB)-I and TiO2 (TB)-II polymorphs, which have enormous 1D channels that provide suitable pathways for mobile ion transport. All structural, electronic properties were consistent with those in literature and all elastic properties agreed excellently with those that were calculated using DFT methods. Finally, the bulk structures of the two polymorphs, were lithiated and sodiated versions and electronic and structural properties were studied, together with the lithiated versions of associated nanostructures consisting of a large number of atoms. Generally, the TiO2 (TB)-I structure was found to be mechanically, energetically more stable and ductile than TiO2 (TB)-II. Hence, it will be beneficial to use TiO2 (TB)-I as an anode material for sodium ion batteries (SIB), due to its unique ductility and larger 1D channels. / National Research Fund (NRF), Department of Science and Innovation (DSI), Material Modelling Centre

<p>Repeatable methods for introducing minor defects in commercial Li-ion pouch cells were developed and different studies were conducted to compare the different signatures that would provide information regarding the factors that are most critical to detect the onset of internal short circuit for each defect test. The cells were subjected to overcharge, over-discharge, nail indentation and heating defect tests. After defect introduction, three different studies – cycling, thermal runaway, and self-discharge were performed on the cells. The overcharge defect case showed signatures in all three studies with the major cause of these signatures being lithium dendrite formation that led to reduction in capacity. The overcharge case was also unique in that it showed recovery in capacity due to lithium stripping process and had the highest temperature recorded which proves that it had the most dangerous defect case. The over-discharge case showed signs of possible copper deposition on the anode side which was evident by the presence of lithium plating in patches which could have been due the copper deposition locations becoming active sites for lithium plating. The nail indentation defect case showed signatures in the thermal runaway study by the shortest time it took to go into thermal runaway and in the self-discharge study which was shown by the inability of cells to stay at a stable voltage even at the most stable SOC. The heating defect test showed potential in that it was able to melt the separator near the pouch and that it had a lower temperature for onset of exotherm, but improvements need to be made to get more conclusive results for this defect case.</p>

Rechargeable lithium-ion batteries are a staple of modern society, providing power to a significant portion of the world's electronics and rapidly replacing older power sources. The advent of widely available electric cars with batteries of up to 200 kWh, with an increasing emphasis on fast charging, has only increased their importance. Lithium-ion battery electronic and ionic properties are largely determined by the microstructure of the battery electrode film and can be heavily influenced by relatively small variations in film makeup, including the formation of voids or distribution of carbon and binder. Prior to this research, electrical properties, which are some of the most important characteristics to battery cost, performance, and safety, were either difficult or, in the case of contact resistance, impossible to directly measure. This dissertation focuses on the development and use of a micro-surface probe for measurement and mapping of lithium-ion battery film electronic characteristics. The measurement apparatus, inversion and mapping routines, and experimental data presented provide manufacturers and researchers with a better understanding of battery heterogeneity and the influence of microstructure on electrical properties. The micro-surface probe was used to map spatial variation on both a macro and micro scale; compare physical, electrical, and ionic properties; and validate tests that were previously used to estimate electronic parameters. Experiments on commercial-quality battery electrode films showed higher micro-heterogeneity than was previously assumed by a significant margin. Additionally, electronic and ionic properties were shown to not always be inversely related and some physical explanations for observed variation were explored. Macro-variations were measured and shown to exist across electrode films which were previously assumed to be uniform. Finally a comparison to the mechanical peel test, a common test used in industry as a proxy measurement of electrical contact resistance, proved the peel test to be inconclusive and showed that it will not always accurately reflect electrical properties of films. Direct measurements of both electrical conductivity and contact resistance provide a new and important tool to advance understanding and development of lithium-ion batteries. The magnitude of the measured resistivities and their significant variation demonstrates that a better understanding of film properties is needed and will significantly influence our understanding of modern battery parameters and the effects of manufacturing techniques on battery performance.

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The market for electric vehicles (EV) is growing rapidly. The rise of EVs is most prominent for passenger vehicles, but trucks and busses are also quickly becoming electrified. Scania aims to be the leader of this transition. A central part of the EV is the Lithium-ion battery. In order to use the battery in the most efficient manner a Battery Management System (BMS) is needed. A key part of the BMS is a model that describes the battery as a system where the input is the current and the output is the terminal voltage. The dynamics of the battery is affected by external factors, called scheduling variables, that should be taken in to account in order to acquire an accurate model. This thesis aims to capture this behavior by the identification of a Linear Parameter Varying (LPV) model that has State of Charge (SOC) and temperature as scheduling variables. The LPV model was identified by first performing a set of local system identifications at varying levels of the scheduling variables. From this, a set of different LPV model structures were set up and then optimized with the use of datasets with a wider coverage of the scheduling variables. The results showed that there are clear advantages in using an LPV model compared to a traditional constant model, but that the robustness of the model largely is dependent on the choice of the data used for optimization.

The electric vehicles, as the most promising solution for achieving high fuel economy, have significantly better emission profile than conventional vehicles powered by fossil fuels. However, range anxiety and the limited accessible fast-charging infrastructures mainly restrain the drivers from adopting the electric vehicles that have much higher energy efficiency. Due to the internal and external factors, the cells in the battery pack degrade differently, leading to a usable capacity that is less than the available capacity if they are left unbalanced, which ultimately shortens the driving range. Therefore, an external circuitry, i.e. battery balancing circuit, that manages the unbalanced cells is installed to maximize the usable capacity, and thus, to prolong the driving range. However, the most commonly adopted balancing circuit is the dissipative balancing strategy in the large-scale electric vehicle productions, where the available capacity is underutilized. One of the most efficient redistributive balancing strategies that overcome the drawbacks of the dissipative one is converter-based strategy that monitors and regulates each paralleled-connected cell module. Nevertheless, installing the individual DC-DC converters on each module is not cost-friendly, and thus, reducing the cost of the converter-based balancing system becomes the priority for large adoptions of the redistributive balancing systems in electric vehicles. This thesis proposes a dual-cell link that integrates the functionalities of the auxiliary power module, battery gauging and battery balancing, leading to a low-cost solution comparable with the dissipative balancing. The topological improvements are made achieving 50% less number of the needed converters compared with the existing topologies. In addition, the integration and minimization are the design targets in terms of the main circuit components. The costly components, such as MOSFETs and magnetic components, are curtailed by 62.5%-75% and 50%-100%, respectively, with no sacrifices on the balancing speed. In order to achieve the magnetic integration, the detailed circuit model is developed using average- and small-signal modeling techniques. The design procedure for the half-full bridge converter with the cored transformer is firstly discussed, followed by a further minimized dual-half active bridge converter with a coreless transformer. Following the design procedure, two systems are characterized, built, tested and validated with the real batteries. Not only is the cost reduced, but also the balancing process is facilitated, which is realized by an additional balancing path. A DC current offset between the adjoining cells in one link can be introduced to the circuit by utilizing a normally undesired volt-amp imbalance in the transformer, which provides the extra cell-to-cell balancing path. An asymmetric duty cycle control is proposed to regulate the DC current offset so that the different balancing modes can be achieved. With the enabled cell-to-cell path, the balancing speed can be reduced by 50% compared with the conventional cell-to-stack only balancing methods with a state-of-charge difference of 20% between two adjoining cells. The auxiliary power module requires the proposed converters to work as efficiently as possible within its wide operating range. However, the efficiency of the half-bridge systems drops at light-load conditions due to the loss of the soft-switching capability and high conduction loss. In order to overcome this drawback, the variable frequency modulation is normally preferred. A conduction-loss based control criteria is proposed, inheriting the benefits of the conventional variable frequency modulation while maintaining the optimized conduction loss. It is validated on the converter prototype that the proposed control criteria can achieve 1-2% better efficiency with an extremely simple but robust control logic compared with the critical soft switching.

Aqueous zinc ion storage system has been deemed as one of the most promising alternatives due to its high capacity of zinc metal anode, low cost, and high safety characteristics. Recently, significant attempts have been made to produce highperformance aqueous Zn batteries. (AZBs) and great progress has been achieved. Yet there are a lot of issues still exist and need to be further optimized. In this thesis, we proposed several strategies to tackle these challenges and finally optimize the overall battery performance, including metal anode protection, cathode structural engineering, and rational electrolyte design. In the present thesis, we first developed the ZnF2 layer coated Zn metal anode via a simple plasma treatment method. The plasma treated Zn anode leads to dendrite-free Zn electrodeposition with lower overpotential. Density function theory calculation results demonstrate that the Zn diffusion energy barrier can be greatly reduced on the ZnF2 surface. Benefiting from these merits, the symmetric cell and full cell exhibited much improved electrolchemical performance and stability. Afterthen, We synthesised a layered Mg2+-intercalated V2O5 as the cathode material for AZBs. The large interlayer spacing reachs up to 13.4 A, allowing for efficient Zn2+ (de)insertion. As a result, the porous Mg0.34V2O5・nH2O cathodes can provide high capacities as well as long-term durability. We then recongnized that most of the parasitic side reactions are related to the aqueous electrolyte. We therefore further designed a hybrid electrolyte to realize the anode-free Zn metal batteries. It is demonstrated that in the presence of propylene carbonate, triflate anions are involved in the Zn2+ solvation sheath structure. The unique solvation structure results in the reduction of anions, thus forming a hydrophobic solid electrolyte interphase. Consequently, in the hybrid electrolyte, both Zn anodes and cathodes show excellent stability and reversibility. More importantly, we design an anode-free Zn metal battery, which exhibits good cycling stability (80% capacity retention after 275 cycles at 0.5 mA cm–2).

Li+ ion batteries have been the mainstay of high energy storage devices that have revolutionized the operating life time of consumer electronic devices for the past two decades. However, there is a steady increase in demand for energy storage devices with the ability to store more energy and deliver them at high power at low cost, without comprising safety and lifetime. Li-ion batteries have had significant challenges in increasing the amount of stored energy without affecting the overall lifetime and the ability to deliver stored energy. In order to store and deliver more energy, more lithium ions need to be inserted and extracted from a given electrode (cathode or anode). Upon inserting a large number of Li ions, the crystal lattice of the materials undergo severe mechanical distortions, leading to un-desirable structural changes. This results in underutilization of theoretical energy storage capacities of the electrodes and early failure of the batteries owing to instabilities in the electrode materials. Unlike monovalent Li+ ions, multivalent rechargeable batteries offer a potential solution to the above problems. Multivalent cations, such as Ca2+, are doubly-ionized as opposed to Li+ which is a monovalent cation. The advantages of using Ca2+ ions instead of Li+ ions are multifold. Due to the doubly-ionized nature, only half the number of Ca2+ ions need to be inserted and extracted from a given electrode to store and deliver energy from a high capacity cathode as compared to Li+ ions. This reduces the probability of lattice distortion and un-desirable structural changes, further leading to increased utilization of high theoretical energy storage capacities of the electrodes (cathode and anode). The use of Ca2+ ions also helps in delivering twice the amount of current density as compared to Li+ ions due to its doubly ionized nature. In this work, a set of eight metal hexacyanoferrate compounds were synthesized using the following metal ions: Ba2+, Mn2+, Zn2+, Co2+, Fe3+, Al3+, Sn4+, Mo5+. The resulting metal hexacyanoferrate compounds were subjected to physical characterization using scanning electron microscope (SEM) and powder x-ray diffraction (XRD), to determine physical properties such as size, morphology, unit cell symmetry and unit cell parameters. This was followed by electrochemical characterization utilizing cyclic voltammetry and galvanic cycling, to determine the specific capacity and kinetics involved in the transport of Ca2+ ions to store charge. Optical characterization of the metal hexacyanoferrates using Fourier transform infrared (FTIR) spectroscopy, allowed for the identification of metal-nitrogen stretching frequency, which was used as a measure of the strength of the metal-nitrogen bond to understand the role of the above mentioned metal ions in electron density distribution across the unit cell of the metal hexacyanoferrates. The specific capacity utilization of the metal hexacyanoferrates, when compared to the electronegativity values (Xi) of the above mentioned metal ions, the σ- parameter, and the metal-nitrogen stretching frequency (v), revealed an empirical trend suggesting that the materials (FeHCF, CaCoHCF and CaZnHCF) that possessed intermediates values for the above mentioned parameters demonstrated high capacity utilization (≥50%). Based on these empirical trends, it is hypothesized that a uniform distribution of electron density around a unit cell, as reflected by intermediate values of the electronegativity (Xi) of the above mentioned metal ions, the σ-parameter and the metal-nitrogen stretching frequency (v), results in minimal electrostatic interactions between the intercalating cation and the host unit cell lattice. This results in relatively easy diffusion of the cations, leading to high specific capacity utilization for metal hexacyanoferrate cathodes. These parameters may be used to select high efficiency cathode materials for multivalent batteries.