Intensive efforts have been conducted to realize the reliable interfacial joining of thermoelectric materials and electrode materials with low interfacial contact resistance, which is an essential step to make thermoelectric materials into thermoelectric devices for industrial application. In this review, the roles of structural integrity, interdiffusion, and contact resistance in long-term reliabilities of thermoelectric modules are outlined first. Then interfacial reactions of near-room-temperature Bi2Te3-based thermoelectric materials and various electrode materials are reviewed comprehensively. We also summarized the joining behavior of the mid-temperature PbTe-based thermoelectric materials and commonly used electrode materials. Subsequently, for other thermoelectric materials systems, i.e., SiGe, CoSb3, and Mg3Sb2, previous attempts to join with some electrode materials are also recapitulated. Finally, some future prospects to further improve the joint reliability in thermoelectric device manufacturing are proposed. We believe that this review will provide guidance for preparing thermoelectric devices and optimizing thermoelectric device design.

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