Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening

Dan Han; Bonan Zhu; Zenghua Cai; Kieran B. Spooner; Stefan S. Rudel; Wolfgang Schnick; Thomas Bein; David O. Scanlon; Hubert Ebert

doi:10.1016/j.matt.2023.10.022

Discovery of multi-anion antiperovskites X₆NFSn₂ (X = Ca, Sr) as promising thermoelectric materials by computational screening

Dan Han^*, Bonan Zhu, Zenghua Cai, Kieran B. Spooner, Stefan S. Rudel, Wolfgang Schnick, Thomas Bein, David O. Scanlon^*, Hubert Ebert

^*Corresponding author for this work

Chemistry

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Abstract

The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X₆NFSn₂ (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca₆NFSn₂ and Sr₆NFSn₂ exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (<1 W m⁻¹ K⁻¹). Notably, Ca₆NFSn₂ and Sr₆NFSn₂ show remarkably larger electrical conductivities compared to the halide perovskite CsSnI₃. The combined superior electrical and thermal properties of Ca₆NFSn₂ and Sr₆NFSn₂ lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X₆NFSn₂ (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.

Original language	English
Pages (from-to)	158-174
Number of pages	17
Journal	Matter
Volume	7
Issue number	1
Early online date	15 Nov 2023
DOIs	https://doi.org/10.1016/j.matt.2023.10.022
Publication status	Published - 3 Jan 2024

Bibliographical note

Acknowledgments:
D.H., H.E., S.S.R., W.S., and T.B. acknowledge support from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy (Excellence Cluster e-conversion--EXC 2089/1--390776260). K.B.S. and D.O.S. acknowledge support from the European Research Council (grant 758345). D.H. and H.E. gratefully acknowledge the Gauss Centre for Supercomputing e.V. (https://www.gauss-centre.eu) for funding this project by providing computing time on the GCS Supercomputer SuperMUC-NG at the Leibniz Supercomputing Centre (https://www.lrz.de). B.Z. acknowledges the use of the UCL Myriad High Performance Computing Facility (Myriad@UCL) and the ARCHER2 UK National Supercomputing Service (http://www.archer2.ac.uk), which is supported by the HEC Materials Chemistry Consortium funded by EPSRC (EP/R029431). D.H. and D.O.S. acknowledge the use of the University of Birmingham BlueBEAR HPC service, which provides a High Performance Computing service to the University's research community. See http://www.birmingham.ac.uk/bear for more details.

Keywords

multi-anion antiperovskite
thermoelectric properties
lattice thermal conductivity
electrical conductivity
figure of merit
weak chemical bonding
bond anharmonicity

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title = "Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening",

abstract = "The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X6NFSn2 (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca6NFSn2 and Sr6NFSn2 exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (<1 W m−1 K−1). Notably, Ca6NFSn2 and Sr6NFSn2 show remarkably larger electrical conductivities compared to the halide perovskite CsSnI3. The combined superior electrical and thermal properties of Ca6NFSn2 and Sr6NFSn2 lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.",

keywords = "multi-anion antiperovskite, thermoelectric properties, lattice thermal conductivity, electrical conductivity, figure of merit, weak chemical bonding, bond anharmonicity",

author = "Dan Han and Bonan Zhu and Zenghua Cai and Spooner, {Kieran B.} and Rudel, {Stefan S.} and Wolfgang Schnick and Thomas Bein and Scanlon, {David O.} and Hubert Ebert",

note = "Acknowledgments: D.H., H.E., S.S.R., W.S., and T.B. acknowledge support from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany{\textquoteright}s Excellence Strategy (Excellence Cluster e-conversion--EXC 2089/1--390776260). K.B.S. and D.O.S. acknowledge support from the European Research Council (grant 758345). D.H. and H.E. gratefully acknowledge the Gauss Centre for Supercomputing e.V. (https://www.gauss-centre.eu) for funding this project by providing computing time on the GCS Supercomputer SuperMUC-NG at the Leibniz Supercomputing Centre (https://www.lrz.de). B.Z. acknowledges the use of the UCL Myriad High Performance Computing Facility (Myriad@UCL) and the ARCHER2 UK National Supercomputing Service (http://www.archer2.ac.uk), which is supported by the HEC Materials Chemistry Consortium funded by EPSRC (EP/R029431). D.H. and D.O.S. acknowledge the use of the University of Birmingham BlueBEAR HPC service, which provides a High Performance Computing service to the University's research community. See http://www.birmingham.ac.uk/bear for more details.",

year = "2024",

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doi = "10.1016/j.matt.2023.10.022",

language = "English",

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journal = "Matter",

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T1 - Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening

AU - Han, Dan

AU - Zhu, Bonan

AU - Cai, Zenghua

AU - Spooner, Kieran B.

AU - Rudel, Stefan S.

AU - Schnick, Wolfgang

AU - Bein, Thomas

AU - Scanlon, David O.

AU - Ebert, Hubert

N1 - Acknowledgments: D.H., H.E., S.S.R., W.S., and T.B. acknowledge support from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy (Excellence Cluster e-conversion--EXC 2089/1--390776260). K.B.S. and D.O.S. acknowledge support from the European Research Council (grant 758345). D.H. and H.E. gratefully acknowledge the Gauss Centre for Supercomputing e.V. (https://www.gauss-centre.eu) for funding this project by providing computing time on the GCS Supercomputer SuperMUC-NG at the Leibniz Supercomputing Centre (https://www.lrz.de). B.Z. acknowledges the use of the UCL Myriad High Performance Computing Facility (Myriad@UCL) and the ARCHER2 UK National Supercomputing Service (http://www.archer2.ac.uk), which is supported by the HEC Materials Chemistry Consortium funded by EPSRC (EP/R029431). D.H. and D.O.S. acknowledge the use of the University of Birmingham BlueBEAR HPC service, which provides a High Performance Computing service to the University's research community. See http://www.birmingham.ac.uk/bear for more details.

PY - 2024/1/3

Y1 - 2024/1/3

N2 - The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X6NFSn2 (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca6NFSn2 and Sr6NFSn2 exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (<1 W m−1 K−1). Notably, Ca6NFSn2 and Sr6NFSn2 show remarkably larger electrical conductivities compared to the halide perovskite CsSnI3. The combined superior electrical and thermal properties of Ca6NFSn2 and Sr6NFSn2 lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.

AB - The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X6NFSn2 (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca6NFSn2 and Sr6NFSn2 exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (<1 W m−1 K−1). Notably, Ca6NFSn2 and Sr6NFSn2 show remarkably larger electrical conductivities compared to the halide perovskite CsSnI3. The combined superior electrical and thermal properties of Ca6NFSn2 and Sr6NFSn2 lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.

KW - multi-anion antiperovskite

KW - thermoelectric properties

KW - lattice thermal conductivity

KW - electrical conductivity

KW - figure of merit

KW - weak chemical bonding

KW - bond anharmonicity

U2 - 10.1016/j.matt.2023.10.022

DO - 10.1016/j.matt.2023.10.022

M3 - Article

SN - 2590-2385

VL - 7

SP - 158

EP - 174

JO - Matter

JF - Matter

IS - 1

ER -

Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening