High-Entropy Skutterudites as Thermoelectrics: Potential Synthesizability, Enhanced Stability, and Band Convergence via the Cocktail Effect

High-entropy materials offer a promising avenue for thermoelectric materials discovery, design, and optimization. However, the large chemical spaces that need to be explored hamper their development. In this work, a large family of high-entropy skutterudites is explored as promising thermoelectric materials. Their potential synthesizability is screened and rationalized using the disordered enthalpy-entropy descriptor through high-throughput density functional theory calculations. In the case of high-entropy skutterudites, the thermodynamic density of states and the entropy gain parameter appear to be key factors for their stabilization. Electronic band structure analyses not only show a reduction in the band gap, which enhances carrier concentration and electrical conductivity, but also a band convergence phenomenon for some specific compositions, which is related to the “cocktail effect.” Analyzing atom-projected band structures shows how band convergence is due to the simultaneous presence of <a:math xmlns:a="http://www.w3.org/1998/Math/MathML" display="inline"> <a:mi>Fe</a:mi> </a:math> , <c:math xmlns:c="http://www.w3.org/1998/Math/MathML" display="inline"> <c:mi>Ni</c:mi> </c:math> , and <e:math xmlns:e="http://www.w3.org/1998/Math/MathML" display="inline"> <e:mi>Co</e:mi> </e:math> in the compound. The presence of <g:math xmlns:g="http://www.w3.org/1998/Math/MathML" display="inline"> <g:mi>Rh</g:mi> </g:math> or <i:math xmlns:i="http://www.w3.org/1998/Math/MathML" display="inline"> <i:mi>Ir</i:mi> </i:math> , while not contributing to this band-convergence effect, can be directly linked to an increase in the system’s entropy, which enhances the thermodynamic stability of these materials. Transport properties are computed for the most promising compositions, and their dynamical, mechanical, and thermal stability are addressed. Our results demonstrate that these types of compounds open new avenues, not only to enhance thermoelectric efficiency but also to reduce costs by utilizing more abundant elements and also improving their durability.