Thermoelectric devices and associated materials and assembly methods are generally described. Certain aspects relate to electrode materials and electrode configurations for use in thermoelectric devices. In some embodiments, the inventive thermoelectric devices comprise electrodes comprising silicon, such as silicides of cobalt, iron, and/or nickel. Such electrode materials can be useful for making electrical contact with a wide variety of thermoelectric materials, including skutterudite materials. The thermoelectric devices described herein can be used to convert applied voltages to thermal gradients and or to convert thermal gradients to electricity.
 This invention was made with government support under Grant Nos. DE-SC0001299 and DE-FG02-09ER46577 awarded by the Department of Energy. The government has certain rights in this invention.