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

TL;DR

This study explores high-entropy skutterudites as thermoelectric materials, demonstrating their potential for improved stability, band convergence, and cost reduction through high-throughput calculations and electronic structure analysis.

Contribution

It introduces a systematic approach to screening and analyzing high-entropy skutterudites, revealing mechanisms for stability and electronic improvements via the cocktail effect.

Findings

High-entropy skutterudites can be stabilized thermodynamically.

Band convergence is achieved through specific elemental combinations.

Presence of Rh or Ir increases entropy and stability.

Abstract

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 Fe, Ni, and Co in the compound. The presence of Rh or Ir, while not contributing to this band convergence effect, can be directly linked to an increase in 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 demonstrates 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.