<p>In the United States, buildings are responsible for almost 40% of the country’s total energy consumption and 38% of the total greenhouse gas emissions. Researchers are constantly seeking sustainable and efficient energy generation solutions for buildings as society continues to cope with the intensifying energy crisis and environmental deterioration. Thermoelectric technology is one such solution that potentially can lead to significant energy recovery and conversion between waste or excess thermal energy and electrical energy. One promising application is integrating thermoelectric materials into the building envelope (TBE) for power generation and building heating and cooling without transporting energy among subsystems and refrigerant use. TBE can combine structural support and thermal storage with power generation and thermal-activated cooling and heating, thereby contributing to sustainable living and energy. </p> <p>TBE technology is still in its early development stages. This dissertation aimed to develop a fundamental understanding of the characteristics, behaviors, operation, and control of TBE systems as energy-efficient measures for thermal energy harvesting and thermal comfort regulation and to address the significant research gaps concerning high-conversion efficiency materials and optimal module configuration as well as system deployment related to real-world applications. Accordingly, this dissertation focused on the following three key objectives: (1) development and characterization of new thermoelectric composite materials; (2) identification of optimal designs and controls of TBE and established mathematical models for performance simulation; and (3) quantification of the energy-saving benefits of TBE. </p> <p>The following five aspects specifically were investigated:</p> <p>(1)<em> Material development and characterization</em>. New thermoelectric cement composites were developed with cement and various additives, material concentrations, and fabrication methods in the laboratory. Their thermoelectric properties (e.g., Seebeck coefficient, thermal conductivity, electrical conductivity, power factor, and the figure of merit) were measured simultaneously and characterized at 300–350 K.</p> <p>(2)<em> Module evaluation.</em> Commercially available thermoelectric modules (TEMs) were assessed using well-designed test apparatus in both the heat pumping and power generation modes. The test results validated the numerical model, which assisted with performance comparison and material selection between cement-based and commercial TEMs for the TBE prototype.</p> <p>(3)<em> Prototype assessment. </em>A convective TBE prototype and a radiant TBE prototype were designed, assembled, and evaluated in a pair of controlled testing chambers. The TBE’s surface temperature, thermal capacity, and COP were assessed under summer and winter conditions. </p> <p>(4)<em> Prototype modeling. </em>The first-principle-based numerical models of both the convective and radiant TBE prototypes were developed in Modelica. The modeling results indicated good agreement with the experimental data. The verified models were used to study the impacts of the design parameters and operating conditions on the heat pumping performance of TBE.</p> <p>(5)<em> System simulation. </em>A TBE building system model was established by integrating the TBE prototype model within a building’s heat balance model, considering the building construction, climate condition, power control, etc. Its seasonal performance under various climate conditions was studied to identify the potential optimal operation and energy savings. </p> <p>This dissertation confirmed several key findings in the areas of material development, system design and operation, and energy savings. The TBE achieved higher efficiency with a heat pump for heating than for cooling generally. The TBE heating system performed better than a conventional electric heater (efficiency assumed at 0.9). The measures that improved TBE heating efficiency were enhancing the material’s thermoelectric properties, optimizing the geometry and number of TEMs, and improving the boundary heat transfer of TEMs. </p> <p>This dissertation concluded that the TBE system is a promising alternative to conventional heating systems in buildings. Furthermore, the knowledge gained will strengthen the understanding of thermoelectrics in the building domain and guide further development in TBE, as well as facilitate the operation of net-zero energy and carbon-neutral buildings. </p>