Al_xCoCrFeNi High-Entropy Alloys Enable Simultaneous Electrical and Mechanical Robustness at Thermoelectric Interfaces

The interface between high-performance thermoelectric materials and electrodes critically governs the conversion efficiency and long-term reliability of thermoelectric generators under high-temperature operation. Here, we propose Al_xCoCrFeNi high-entropy alloys (HEA) as barrier layers to bond Cu-W electrodes with p-type skutterudite (p-SKD) thermoelectric materials. The HEA/p-SKD interface exhibited excellent chemical bonding with a stable and controllable reaction layer, forming a dense, defect-free (Fe,Ni,Co,Cr)Sb phase (thickness of ~2.5 μm) at the skutterudites side. The interfacial resistivity achieved a low value of 0.26 μΩ·cm² and remained at 7.15 μΩ·cm² after aging at 773 K for 16 days. Moreover, the interface demonstrated remarkable mechanical stability, with an initial shear strength of 88 MPa. After long-term aging for 16 days at 773 K, the shear strength retained 74 MPa (only 16% degradation), ranking among the highest reported for thermoelectric materials/metal joints. Remarkably, the joint maintained a shear strength of 29 MPa even after 100 continuous thermal cycles (623-773 K), highlighting its outstanding thermo-mechanical stability. These results validate the Al_xCoCrFeNi high-entropy alloys as an ideal interfacial material for thermoelectric generators, enabling simultaneous optimization of electrical and mechanical performance in harsh environments.