Understanding the thermally activated charge transport in NaPbmSbQm+2 (Q = S, Se, Te) thermoelectrics: weak dielectric screening leads to grain boundary dominated charge carrier scattering

Slade, Tyler J.; Grovogui, Jann A.; Kuo, Jimmy Jiahong; Anand, Shashwat; Bailey, Trevor P.; Wood, Maxwell; Uher, Ctirad; Snyder, G. Jeffrey; Dravid, Vinayak P.; Kanatzidis, Mercouri G.

doi:10.1039/d0ee00491j

Understanding the thermally activated charge transport in NaPb_mSbQ_m+2 (Q = S, Se, Te) thermoelectrics: weak dielectric screening leads to grain boundary dominated charge carrier scattering

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d0ee00491j· OSTI ID:1778878

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Northwestern Univ., Evanston, IL (United States); Northwestern University
Northwestern Univ., Evanston, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)

Many thermoelectric materials feature irregular electrical conductivity with thermally activated transport below ~600 K and metallic behavior at high temperatures, despite possessing degenerate carrier concentrations. The suppression of the electrical conductivity ultimately degrades the thermoelectric performance on the cold side and limits the device energy conversion efficiency. As such, establishing the origin of the low temperature scattering and developing strategies to mitigate its effect are paramount issues. To date, the correct microscopic description of the low temperature carrier scattering remains an open issue, and there is little work addressing why some thermoelectric materials are more susceptible to the deleterious behavior. Here, we use the promising thermoelectric alloys of PbQ and NaSbQ₂ (Q = S, Se, Te) as model systems to address these concerns. We directly show the thermally activated transport stems from the scattering of charge carriers by the grain boundaries (GBs), and that the expected metallic electrical conductivity is recovered by preparing large grained samples with reduced densities of GBs. We furthermore study the electrical properties NaPb_mSbSe_m+2 as a function of NaSbSe₂ fraction, as well as those of the chalcogenide analogues, PbTe–NaSbTe₂ and PbS–NaSbS₂, and demonstrate that the strength of GB scattering can be understood by utilizing simple chemical principles. By considering the polarizability of the host atoms, we directly relate the magnitude of GB scattering to the relative degree of charge carrier screening in each material, and demonstrate that GB scattering is strongest in the ionic NaSbQ₂-rich compounds and weakest in more polarizable PbQ-rich phases. We finally show how these chemical arguments elegantly explain the strong GB scattering in numerous other thermoelectric materials. By uniting the deleterious charge transport properties exhibited by many different compounds into a common picture, we discuss how our work gives design principles for proper microstructure engineering in emerging thermoelectric materials.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014520

OSTI ID:: 1778878

Alternate ID(s):: OSTI ID: 1615041

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 5 Vol. 13; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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