This article discusses the characteristics of the design of thermoelectric generators (TEGs) for cold climates. Since the thermocouples of thermoelectric batteries are produced from different materials, their major properties are studied. Particular attention is given to nanostructured materials regarding the modern class of thermoelectric materials. Two-, three-, and four-component alloys (metallic glasses) of the Fe-Ni(Cu)-P-B system are chosen based on the experience of thermoelectric thermometry. The close chemical composition of two thermoelectrodes enables their compatibility in thermocouple production and satisfactory thermoelectric efficiency of batteries during long-term operation. The improvement of the thermoelectric battery characteristics related to a unit of mass is evaluated. The materials studied are distinguished by the absence of toxic components harmful to the environment at the manufacturing and operating stages.