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.

Geothermal district heating networks: modelling novel operational strategies incorporating heat storage

The value of integrating a heat storage into a geothermal district heating system has been investigated. The behaviour of the system under a novel operational strategy has been simulated focusing on the energetic, economic and environmental effects of the new strategy of incorporation of the heat storage within the system. A typical geothermal district heating system consists of several production wells, a system of pipelines for the transportation of the hot water to end-users, one or more re-injection wells and peak-up devices (usually fossil-fuel boilers). Traditionally in these systems, the production wells change their production rate throughout the day according to heat demand, and if their maximum capacity is exceeded the peak-up devices are used to meet the balance of the heat demand. In this study, it is proposed to maintain a constant geothermal production and add heat storage into the network. Subsequently, hot water will be stored when heat demand is lower than the production and the stored hot water will be released into the system to cover the peak demands (or part of these). It is not intended to totally phase-out the peak-up devices, but to decrease their use, as these will often be installed anyway for back-up purposes. Both the integration of a heat storage in such a system as well as the novel operational strategy are the main novelties of this thesis. A robust algorithm for the sizing of these systems has been developed. The main inputs are the geothermal production data, the heat demand data throughout one year or more and the topology of the installation. The outputs are the sizing of the whole system, including the necessary number of production wells, the size of the heat storage and the dimensions of the pipelines amongst others. The results provide several useful insights into the initial design considerations for these systems, emphasizing particularly the importance of heat losses. Simulations are carried out for three different cases of sizing of the installation (small, medium and large) to examine the influence of system scale. In the second phase of work, two algorithms are developed which study in detail the operation of the installation throughout a random day and a whole year, respectively. The first algorithm can be a potentially powerful tool for the operators of the installation, who can know a priori how to operate the installation on a random day given the heat demand. The second algorithm is used to obtain the amount of electricity used by the pumps as well as the amount of fuel used by the peak-up boilers over a whole year. These comprise the main operational costs of the installation and are among the main inputs of the third part of the study. In the third part of the study, an integrated energetic, economic and environmental analysis of the studied installation is carried out together with a comparison with the traditional case. The results show that by implementing heat storage under the novel operational strategy, heat is generated more cheaply as all the financial indices improve, more geothermal energy is utilised and less fuel is used in the peak-up boilers, with subsequent environmental benefits, when compared to the traditional case. Furthermore, it is shown that the most attractive case of sizing is the large one, although the addition of the heat storage most greatly impacts the medium case of sizing. In other words, the geothermal component of the installation should be sized as large as possible. This analysis indicates that the proposed solution is beneficial from energetic, economic, and environmental perspectives. Therefore, it can be stated that the aim of this study is achieved in its full potential. Furthermore, the new models for the sizing, operation and economic/energetic/environmental analyses of these kind of systems can be used with few adaptations for real cases, making the practical applicability of this study evident. Having this study as a starting point, further work could include the integration of these systems with end-user demands, further analysis of component parts of the installation (such as the heat exchangers) and the integration of a heat pump to maximise utilisation of geothermal energy.