Thermoelectric devices are capable of converting thermal energy directly into electrical energy. The efficiency of a device is related to the characteristics of the materials of which it is composed. Large-scale applications of the technology requires materials that are composed of earth-abundant elements. Here we seek to exploit the capabilities of a novel sample cell to carry out the first in-situ study of thermoelectric materials in which the key electrical properties of resistivity and Seebeck coefficient will be measured simultaneously with the collection of structural data by powder neutron diffraction. Two synthetic analogues of copper chalcogenide minerals will be investigated in an effort to understand the underlying structural basis for the marked changes in electrical properties that occur when the material undergoes structural phase transitions on heating.