Challenges Reconciling Theory and Experiments in the Prediction of Lattice Thermal Conductivity: The Case of Cu-Based Sulvanites

Abstract

The exploration of large chemical spaces in search of new thermoelectric materials requires the integration of experiments, theory, simulations, and data science. The development of high-throughput strategies that combine DFT calculations with machine learning has emerged as a powerful approach to discovering new materials. However, experimental validation is crucial to confirm the accuracy of these workflows. This validation becomes especially important in understanding the transport properties that govern the thermoelectric performance of materials since they are highly influenced by synthetic, processing, and operating conditions. In this work, we explore the thermal conductivity of Cu-based sulvanites by using a combination of theoretical and experimental methods. Previous discrepancies and significant variations in reported data for Cu₃VS₄ and Cu₃VSe₄ are explained using the Boltzmann Transport Equation for phonons and by synthesizing well-characterized defect-free samples. The use of machine learning approaches for extracting high-order force constants opens doors to charting the lattice thermal conductivity across the entire Cu-based sulvanite family─finding not only materials with κ_l values below 2 W m^–1 K^–1 at moderate temperatures but also rationalizing their thermal transport properties based on chemical composition.