Developing high-efficiency multiphase thermoelectric materials

This thesis explores strategies for improving the efficiency of thermoelectric materials, with a particular focus on multiphase bismuth chalcogenide compounds. The introduction and literature review provide the necessary background on thermoelectricity and its applications, define key parameters such as the dimensionless figure of merit zT, and outline established methods for optimising single and multiphase thermoelectric materials. The literature review chapter delves into important concepts and mechanisms such as energy filtering, modulation doping, and phonon scattering in multiphase systems. The experimental methods chapter then outlines the different material synthesis techniques used, such as melting, ball milling, and spark plasma sintering, as well as the analytical approaches used to study the materials, including structural, electronic, and thermal transport characterisation. The subsequent results chapters examine the effects of incorporating magnetic dopants and secondary phases into bismuth sulphide, telluride, and selenide host systems. A notable finding was that magnetic co-doping of Bi2S3 with chromium and chlorine significantly increased the thermopower and power factor, attributed to a magnetic drag effect that increases the effective carrier mass. The addition of a Bi14Te13S8 secondary phase to Bi2Te3 matrix compounds was also investigated; the presence of this phase led to an energy filtering effect that improved the thermopower but also introduced additional phonon scattering at phase interfaces that reduced the lattice thermal conductivity. Further studies of sulphur-containing Bi2Te2.7Se0.3 revealed that sulphur inclusion dramatically alters the density of states and native defect concentrations in both single and multiphase samples. Interestingly, multiphase Bi2Te2.7Se0.3 samples exhibited complex electronic behaviour, suggesting possible impurity band formation at higher secondary phase contents. Further investigations Bi0.5Sb1.5Te3 with added CrSb compounds showed that small amounts of the magnetic secondary phase increased the thermopower via an increased effective mass, but higher CrSb contents degraded the performance due to reduced carrier mobility. Finally, iodine doping of single phase Bi14Te13S8, an important component of the multiphase materials studied, was found to effectively optimise the power factor and reduce the lattice thermal conductivity, culminating in an improved figure of merit zT. In summary, this work provides compelling evidence that strategies such as energy filtering, modulation doping, and phonon scattering can be successfully exploited to improve the efficiency of multiphase bismuth chalcogenide thermoelectric materials. The results provide valuable insights to guide ongoing research and development efforts towards higher performance thermoelectric materials for real-world applications

Recent Progress in Multiphase Thermoelectric Materials

Thermoelectric materials, which directly convert thermal energy to electricity and vice versa, are considered a viable source of renewable energy. However, the enhancement of conversion efficiency in these materials is very challenging. Recently, multiphase thermoelectric materials have presented themselves as the most promising materials to achieve higher thermoelectric efficiencies than single-phase compounds. These materials provide higher degrees of freedom to design new compounds and adopt new approaches to enhance the electronic transport properties of thermoelectric materials. Here, we have summarised the current developments in multiphase thermoelectric materials, exploiting the beneficial effects of secondary phases, and reviewed the principal mechanisms explaining the enhanced conversion efficiency in these materials. This includes energy filtering, modulation doping, phonon scattering, and magnetic effects. This work assists researchers to design new high-performance thermoelectric materials by providing common concepts

Room-Temperature Thermoelectric Performance of n‑Type Multiphase Pseudobinary Bi 2 Te 3 –Bi 2 S 3 Compounds: Synergic Effects of Phonon Scattering and Energy Filtering

Bismuth telluride-based alloys possess the highest efficiencies for the low-temperature-range (<500 K) applications among thermoelectric materials. Despite significant advances in the efficiency of p-type Bi2Te3-based materials through engineering the electronic band structure by convergence of multiple bands, the n-type pair still suffers from poor efficiency due to a lower number of electron pockets near the conduction band edge than the valence band. To overcome the persistent low efficiency of n-type Bi2Te3-based materials, we have fabricated multiphase pseudobinary Bi2Te3–Bi2S3 compounds to take advantages of phonon scattering and energy filtering at interfaces, enhancing the efficiency of these materials. The energy barrier generated at the interface of the secondary phase of Bi14Te13S8 in the Bi2Te3 matrix resulted in a higher Seebeck coefficient and consequently a higher power factor in multiphase compounds than the single-phase alloys. This effect was combined with low thermal conductivity achieved through phonon scattering at the interfaces of finely structured multiphase compounds and resulted in a relatively high thermoelectric figure of merit of ∼0.7 over the 300–550 K temperature range for the multiphase sample of n-type Bi2Te2.75S0.25, double the efficiency of single-phase Bi2Te3. Our results inform an alternative alloy design to enhance the performance of thermoelectric materials

Recent Progress in Multiphase Thermoelectric Materials

Thermoelectric materials, which directly convert thermal energy to electricity and vice versa, are considered a viable source of renewable energy. However, the enhancement of conversion efficiency in these materials is very challenging. Recently, multiphase thermoelectric materials have presented themselves as the most promising materials to achieve higher thermoelectric efficiencies than single-phase compounds. These materials provide higher degrees of freedom to design new compounds and adopt new approaches to enhance the electronic transport properties of thermoelectric materials. Here, we have summarised the current developments in multiphase thermoelectric materials, exploiting the beneficial effects of secondary phases, and reviewed the principal mechanisms explaining the enhanced conversion efficiency in these materials. This includes energy filtering, modulation doping, phonon scattering, and magnetic effects. This work assists researchers to design new high-performance thermoelectric materials by providing common concepts

Considerando incertezas na análise de estabilidade transitória em sistemas elétricos de potência

Alternative renewable energy sources such as solar, wind, and bio energy have brought uncertainties into the power flow of electric power systems. Purely deterministic tools and models are suitable to guarantee the safe operation of these systems. A necessity arises to develop and use methods that deal with uncertainties in the analysis. Several methodologies have been proposed to assess the transient stability of power systems considering uncertainties. However, most of these techniques are based on the execution of successive simulations, requiring a high computational effort. Hence, they are limited to off-line applications in small systems. In view of the foregoing, this work proposes the development of two methodologies to assess &#8211; in real time &#8211; the transient stability of power systems with parametric and operational uncertainties. The first one is an extension of PEBS, which is a direct method for stability assessment. This method, called robust PEBS, employs an interval energy function of the power system to determine a robust estimate critical clearing time. The second one is the use of optimization methods to find a robust estimate critical clearing time. Notably, we employ the Simulated Annealing and Differential Evolution algorithms. Besides developing methods to estimate the critical clearing time, this work also contributes to the analysis of power systems with uncertainties by introducing a technique to reduce the analysis effort. To be specific, a methodology is proposed to identify the most influential parameters for the transient analysis assessment based on a sensitivity analysis of the generator angles with respect to the system parameters.A utilização crescente de fontes alternativas intermitentes de energia como eólica e solar tem trazido incertezas em relação ao nível de geração e ao fluxo de potência em Sistemas Elétricos de Potência (SEP). Assim, a utilização de modelagem e ferramentas puramente determinísticas na análise de estabilidade não são mais suficientes para garantir a operação segura destes sistemas. Torna-se necessário, então, o desenvolvimento e utilização de métodos que incluam essas incertezas nas análises. Diversas metodologias foram propostas para avaliar a estabilidade transitória de Sistemas Elétricos de Potência considerando incertezas. Porém, grande parte destas técnicas é baseada em execuções de inúmeras simulações e, portanto, exige grande esforços computacionais e são limitadas a aplicações off-line e em sistemas elétricos de pequeno porte. Face ao exposto, propõe-se o desenvolvimento de uma metodologia rápida para a avaliação de estabilidade transitória de SEPs em tempo real considerando incertezas paramétricas. Esta metodologia deverá ser capaz de fornecer rapidamente um resultado robusto sobre a estabilidade. Para tal pretende-se estender a aplicação do método direto PEBS para a análise de estabilidade de sistemas elétricos com incertezas. Além disso, neste trabalho, aplicam-se métodos de otimização para se encontrar o tempo crítico de abertura sem o uso de uma simulação de Monte Carlo e determinam-se os parâmetros que mais influenciam para o estudo de estabilidade transitória utilizando uma análise de sensibilidade dos ângulos dos geradores em relação aos parâmetros do sistema elétrico de potência

Digital light processing additive manufacturing of in situ mullite-zirconia composites

Digital light processing (DLP) can produce small series ceramic parts with complex geometries and tiny structures without the high cost of molds usually associated with traditional ceramic processing. However, the availability of feedstock of different ceramics for the technique is still limited. Mullite-zirconia composites are refractory materials with diverse applications, nevertheless, their 3D printing has never been reported. In this work, alumina and zircon were used as raw materials for additive manufacturing by DLP followed by in situ mullite and zirconia formation. Thus, coarse zircon powder was milled to submicrometric size, alumina-zircon photosensitive slurries were prepared and characterized, parts were manufactured in a commercial DLP 3D printer, debound, and sintered at different temperatures. The printed parts sintered at 1600 °C completed the reaction sintering and reached a flexural strength of 84 ± 13 MPa. The process proved capable of producing detailed parts that would be unfeasible by other manufacturing methods