Beyond Rattling: Tetrahedrites as Incipient Ionic Conductors.

Materials with ultralow thermal conductivity are crucial to many technological applications, including thermoelectric energy harvesting, thermal barrier coatings, and optoelectronics. Liquid-like mobile ions are effective at disrupting phonon propagation, hence suppressing thermal conduction. However, high ionic mobility leads to degradation of liquid-like thermoelectric materials under operating conditions due to ion migration and metal deposition at the cathode, hindering their practical application. Here, we identify a new type of behaviour, incipient ionic conduction, which leads to ultralow thermal conductivity, while overcoming the issues of degradation inherent in liquid-like materials. Using neutron spectroscopy and molecular-dynamics simulations, we demonstrate that in tetrahedrite, an established thermoelectric material with a remarkably low thermal conductivity, copper ions although mobile above 200 K, are predominantly confined to cages within the crystal structure. Hence the undesirable migration of cations to the cathode can be avoided. These findings unveil a new approach for the design of materials with ultralow thermal conductivity, by exploring systems in which incipient ionic conduction may be present. This article is protected by copyright. All rights reserved.