Microwave-assisted synthesis and local analyses of positive insertion electrodes for Li-ion batteries

Efficient energy storage holds the key to reducing waste energy and enabling the use of advanced handheld electronic devices, hydrid electric vehicles and residential energy storage. Recently, Li-ion batteries have been identified and employed as energy storage devices due to their high gravimetric and volumetric energy densities, in comparison to previous technologies. However, more research is required to enhance the efficiency of Li-ion batteries by discovering electrodes with larger electrochemical discharge capacities, while maintaining electrochemical stability. The aims of this study are to develop new microwave-assisted synthesis routes to nanostructured insertion cathodes, which harbor a greater affinity for lithium extraction and insertion than bulk materials. Subsequent to this, state-of-the-art synchrotron based techniques have been employed to understand structural and dynamic behaviour of nanostructured cathode materials during battery cell operation. In this study, microwave-assisted routes to a-LiFePO4, VO2(B), V3O7, H2V3O8 and V4O6(OH)4 have all been developed. Muon spin relaxation has shown that the presence of b-LiFePO4 has a detrimental effect on the lithium diffusion properties of a-LiFePO4, in agreement with first principles calculations. For the first time, a-LiFePO4 nanostructures have been obtained by employing a deep eutectic solvent reaction media showing near theoretical capacity (162 mAh g–1). Studies on VO2(B) have shown that the discharge capacity obtained is linked to the synthesis method. Electrochemical studies of H2V3O8 nanowires have shown outstanding discharge capacities (323 mAh g–1 at 100 mA g–1) and rate capability (180 mAh g–1 at 1 A g–1). The electrochemcial properties of V4O6(OH)4 have been investigated for the first time and show a promising discharge capacity of (180 mAh g–1). Lastly, in situ X-ray absorption spectroscopy has been utilised to track the evolution of the oxidation states in a-LiFePO4, VO2(B) and H2V3O8, and has shown these can all be observed dynamically.

NETCODE: an XOR-based warning dissemination scheme for vehicular wireless networks

The next generation of vehicles will be equipped with automated Accident Warning Systems (AWSs) capable of warning neighbouring vehicles about hazards that might lead to accidents. The key enabling technology for these systems is the Vehicular Ad-hoc Networks (VANET) but the dynamics of such networks make the crucial timely delivery of warning messages challenging. While most previously attempted implementations have used broadcast-based data dissemination schemes, these do not cope well as data traffic load or network density increases. This problem of sending warning messages in a timely manner is addressed by employing a network coding technique in this thesis. The proposed NETwork COded DissEmination (NETCODE) is a VANET-based AWS responsible for generating and sending warnings to the vehicles on the road. NETCODE offers an XOR-based data dissemination scheme that sends multiple warning in a single transmission and therefore, reduces the total number of transmissions required to send the same number of warnings that broadcast schemes send. Hence, it reduces contention and collisions in the network improving the delivery time of the warnings. The first part of this research (Chapters 3 and 4) asserts that in order to build a warning system, it is needful to ascertain the system requirements, information to be exchanged, and protocols best suited for communication between vehicles. Therefore, a study of these factors along with a review of existing proposals identifying their strength and weakness is carried out. Then an analysis of existing broadcast-based warning is conducted which concludes that although this is the most straightforward scheme, loading can result an effective collapse, resulting in unacceptably long transmission delays. The second part of this research (Chapter 5) proposes the NETCODE design, including the main contribution of this thesis, a pair of encoding and decoding algorithms that makes the use of an XOR-based technique to reduce transmission overheads and thus allows warnings to get delivered in time. The final part of this research (Chapters 6--8) evaluates the performance of the proposed scheme as to how it reduces the number of transmissions in the network in response to growing data traffic load and network density and investigates its capacity to detect potential accidents. The evaluations use a custom-built simulator to model real-world scenarios such as city areas, junctions, roundabouts, motorways and so on. The study shows that the reduction in the number of transmissions helps reduce competition in the network significantly and this allows vehicles to deliver warning messages more rapidly to their neighbours. It also examines the relative performance of NETCODE when handling both sudden event-driven and longer-term periodic messages in diverse scenarios under stress caused by increasing numbers of vehicles and transmissions per vehicle. This work confirms the thesis' primary contention that XOR-based network coding provides a potential solution on which a more efficient AWS data dissemination scheme can be built.