Synthesis and processing of materials for direct thermal-to-electric energy conversion and storage.

摘要

Currently, fossil fuels are the primary source of energy. Mechanical heat engines convert the chemical potential energy in fossil fuels to useful electrical energy through combustion; a relatively low efficiency process that generates carbon dioxide. This practice has led to a significant increase in carbon dioxide emissions and is contributing to climate change. However, not all heat engines are mechanical. Alternative energy generation technologies to mechanical heat engines are known, yet underutilized. Thermoelectric generators are solid-state devices originally developed by NASA to power deep space spacecraft, which can also convert heat into electricity but without any moving parts. Similar to their mechanical counterparts, any heat source, including the burning of fossil fuels, can be used. However, clean heat sources, such as concentrated solar, can alternatively be used. Since the energy sources for many of the alternative energy technologies is intermittent, including concentrated solar for thermoelectric devices, load matching is difficult or impossible and an energy storage technology is needed in addition to the energy conversion technology. This increases the overall cost and complexity of the systems since two devices are required and represents a significant barrier for mass adoption of an alternative energy technology. However, it is possible to convert heat energy to electrical energy and store excess charge for use at a later time when the demand increases, in a single device. One such of a device is a thermogalvanic generator and is the electrochemical analog of electronic thermoelectric devices. Essentially, a thermogalvanic device represents the combination of thermoelectric and galvanic systems. As such, the rich history of strategies developed by both the thermoelectric community to better the performance of thermoelectric devices and by the electrochemical community to better traditional galvanic devices (i.e. batteries) can be applied to thermogalvanic devices. Although thermogalvanic devices are known, there has been little exploration into the use of thermogalvanic devices for power generation and energy storage.;First, this work formalizes the energy problem and introduces the operating principles of thermoelectric, galvanic, and thermogalvanic devices. Second, oxide based thermoelectric materials are explored from a synthetic and processing standpoint. Out of necessity, a new synthetic technique was invented and a novel hot-press technique was developed. Third, a solid Li-ion conducting electrolyte, based on the garnet crystal structure, is identified for the use in a thermogalvanic cell. In order to better understand the conductivity behavior, an in-depth exploration into the variables that control the ionic transport is performed on the electrolyte. Third, a thermogalvanic cell is constructed using this garnet based Li-ion conducting solid electrolyte and the first demonstration of such a cell is presented. Finally, strategies to improve the performance of thermogalvanic cells based on garnet type solid electrolytes are outlined for future work.;The purpose of this work is to use an interdisciplinary approach to marry together the electrochemistry of galvanic systems with the strategies used to better semiconductor based thermoelectric materials and ceramics processing techniques to fabricate these systems. This dissertation will explore the interplay of these areas.