Nanostructured Thermoelectric Oxides for Energy Generation: A Combined Experimental and Modelling Investigation

The Seebeck effect is a thermoelectric effect whereby a temperature gradient across a material is converted to a voltage, which can be exploited for power generation. The growing concern over fossil fuels and carbon emissions has led to detailed reviews of all aspects of energy generation and routes to reduce consumption. Thermoelectric (TE) technology, utilising the direct conversion of waste heat into electric power, has emerged as a serious contender, particular for automotive and engine related applications. Thermoelectric power modules employ multiple pairs of n-type and p-type TE materials. Traditional metallic TE materials (such as Bi2Te3 and PbTe), available for 50 years, are not well suited to high temperature applications since they are prone to vaporization, surface oxidation, and decomposition. In addition many are toxic. Si-Ge alloys are also well established, with good TE performance at temperatures up to 1200K but the cost per watt can be up to 10x that of conventional materials. In the last decade oxide thermoelectrics have emerged as promising TE candidates, particularly perovskites (such as n-type CaMnO3) and layered cobaltites (e.g. p-type Ca3Co4O9) because of their flexible structure, high temperature stability and encouraging ZT values, but they are not yet commercially viable. Thus this investigation is concerned with understanding and improving the thermoelectric properties of oxide materials based on CaMnO3 and ZnO. Furthermore, not only do they represent very promising n-type materials in their own right but by using them as model materials with different and well-characterised structures we aim to use them to identify quantitatively how different factors control thermoelectric properties.
The conversion efficiency of thermoelectric materials is characterised by the figure of merit ZT (where T is temperature); ZT should be as high as possible. To maximise the Z value requires a high Seebeck coefficient (S), coupled with small thermal conductivity and high electrical conductivity. In principle electrical conductivity can be adjusted by changes in cation/anion composition. The greater challenge is to concurrently reduce thermal conductivity. However in oxide ceramics the lattice conductivity dominates thermal transport since phonons are the main carriers of heat. This affords the basis for a range of strategies for reducing heat conduction; essentially microstructural engineering at the nanoscale to increase phonon scattering. The nanostructuring approaches will be: (i) introduction of foreign ions into the lattice, (ii) development of superlattice structures, (iii) nanocompositing by introducing texture or nm size features (iv) development of controlled porosity of different size and architecture, all providing additional scattering centres. Independently, TE enhancement can also be achieved by substitution of dopants to adjust the electrical conductivity. By systematically investigating the effect of nanostructuring in CaMnO3 and ZnO ceramics, plus the development of self-assembly nanostructures we will be able to define the relative importance of the factors and understand the mechanisms controlling thermal and electron transport in thermoelectric oxides.
A key feature of the work is that we will adopt an integrated approach, combining advanced experimental and modelling techniques to investigate the effect of nanostructured features on the properties of important thermoelectric oxide. The modelling studies will both guide the experimentalists and provide quantitative insight into the controlling mechanisms and processes occurring at the atom level to the grain level, while the experiments will provide a rigorous test of the calculation of the different thermoelectric properties.
We will assess the mechanical performance of optimised n-type and p-type materials, and then construct thermoelectric modules which will be evaluated in automobile test environments.

The work will provide a foundation for the development and exploitation of high temperature thermoelectric ceramics to generate energy via waste heat. The beneficiaries in the commercial sector are threefold: (i) ceramic manufacturers who will have new products, (ii) producers of energy management devices who will be able to develop new products for new high temperature markets, and (iii) users of thermoelectric modules, such as motor manufacturers, generating energy from waste heat. Policy makes will benefit from the research by knowledge of developments of environmentally friendly methods of energy generation and a way to help reduce the use of fossil fuels.
There will be opportunities for museums with exhibits highlighting the principles of thermoelectric power generation and applications from automobiles to domestic environments. To the wider public there will be environmental benefits of utilising oxides in place toxic metal thermoelectrics and from the generation of energy from waste heat, leading to improved fuel consumption for automobiles and economic benefit to individuals and the UK.
The research has the potential to impact the wealth and the economic competitiveness of the UK by the development of enhanced thermoelectric materials and power modules. For UK companies there will be new opportunities and new markets in the production of ceramics, the development of energy management systems, and exploitation of energy generation systems. All companies in the supply chain should become more competitive. With generation of power from waste heat in the automobile and other sectors there will be improved fuel consumption and the potential for reduction of imported oil to the UK, giving additional economic benefits. New thermoelectric power modules should be realised within 3-5 years, bringing benefits to companies in the supply chain within 3-7 years. The wider benefits of effective power generation and potential reduction of oil consumption should come within 5-10 years.
The researchers working on the project will gain transferable skills in materials fabrication, microstructural and functional property characterisation, advanced modelling techniques together with skills in report writing and critical analysis that will be of value in future employment.
We will establish a network linking UK industrial companies relevant to the supply chain, users of power generation modules, plus other academics in the field. Regular contact and news of developments will be circulated via electronic newsletters and a Workshop will be held in year 3 of the project. Non-confidential findings will be published on a project web page. Scientific and technological findings will be disseminated to the academic and industrial communities via presentations at major international conferences and high impact refereed publications.
Our industrial collaborators cover all aspects of the supply chain: Morgan Electroceramics (ceramic producer), ETL (Energy Management), Ricardo (engine designer), Jaguar (vehicle manufacturer) and Rolls Royce (engine manufacturers). Our academic collaborators provide additional expertise: P Colombo (Padova) routes to controlled porosity, M Reece (QMUL) SPS techniques, A Wiedenkaff (EMPA) single crystal growth, J-F Li (Tsinghua) p-type materials. With collaborators we will protect and exploit IP through the University of Manchester Technology Transfer Unit and University of Bath Research Development and Collaborations Unit. The Manchester applicants (RF, CAL) have over twenty years experience of investigating structure-property relationships in electroceramics, including thermoelectric materials; the Bath applicant (SCP) has over thirty years experience of developing and using high level computer codes to investigate the role of phonons, structure and stability of oxides. With academic and industrial collaborators we have the necessary expertise and facilities to successfully undertake the programme of work.