Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering

Abstract Crystals exhibiting glass‐like and low lattice thermal conductivity (κL) are not only scientifically intriguing but also practically valuable in various applications, including thermal barrier coatings, thermoelectric energy conversion, and thermal management. However, such unusual κL are t...

Full description

Saved in:
Bibliographic Details
Main Authors: Zhonghao Xia, Xingchen Shen, Jun Zhou, Yuling Huang, Yali Yang, Jiangang He, Yi Xia
Format: Article
Language:English
Published: Wiley 2025-05-01
Series:Advanced Science
Subjects:
Online Access:https://doi.org/10.1002/advs.202417292
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849324148838367232
author Zhonghao Xia
Xingchen Shen
Jun Zhou
Yuling Huang
Yali Yang
Jiangang He
Yi Xia
author_facet Zhonghao Xia
Xingchen Shen
Jun Zhou
Yuling Huang
Yali Yang
Jiangang He
Yi Xia
author_sort Zhonghao Xia
collection DOAJ
description Abstract Crystals exhibiting glass‐like and low lattice thermal conductivity (κL) are not only scientifically intriguing but also practically valuable in various applications, including thermal barrier coatings, thermoelectric energy conversion, and thermal management. However, such unusual κL are typically observed only in compounds containing heavy elements, with large unit cells, or at high temperatures. In this study, chemical bonding principles are utilized to weaken the Ag–Ag bonds and enhance lattice anharmonicity. The incorporation of a chalcogen anion as a bridge ligand is proposed to facilitate phonon rattling in Ag6‐octahedron‐based compounds. Guided by this design strategy, five Ag6 octahedron‐based compounds, AAg3X2 (A = Li, Na, and K; X = S and Se), which are characterized by low average atomic masses and exhibit exceptionally strong four‐phonon scattering, are theoretically identified. Consequently, these compounds demonstrate ultralow thermal conductivities (0.3–0.6 W m−1 K−1) with minimal temperature dependence (T−0.1) across a wide temperature range. Experimental validation confirms that the κL of NaAg3S2 is 0.45 W m−1 K−1 within the temperature range of 200–550 K. The results clearly demonstrate that weak chemical bonding plays a crucial role in designing compounds with glass‐like κL, highlighting the effectiveness of chemical bonding engineering in achieving desired thermal transport properties.
format Article
id doaj-art-74433ea84c874c639b6f3ccecfa3e19a
institution Kabale University
issn 2198-3844
language English
publishDate 2025-05-01
publisher Wiley
record_format Article
series Advanced Science
spelling doaj-art-74433ea84c874c639b6f3ccecfa3e19a2025-08-20T03:48:47ZengWileyAdvanced Science2198-38442025-05-011217n/an/a10.1002/advs.202417292Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding EngineeringZhonghao Xia0Xingchen Shen1Jun Zhou2Yuling Huang3Yali Yang4Jiangang He5Yi Xia6Key Laboratory of Advanced Materials and Devices for Post‐Moore Chips Ministry of Education School of Mathematics and Physics University of Science and Technology Beijing Beijing 100083 ChinaCRISMAT, CNRS ENSICAEN Caen 14000 FranceBasic Experimental Center for Natural Science University of Science and Technology Beijing Beijing 100083 ChinaDepartment of Mechanical and Energy Engineering Southern University of Science and Technology (SUSTech) Shenzhen 518055 ChinaKey Laboratory of Advanced Materials and Devices for Post‐Moore Chips Ministry of Education School of Mathematics and Physics University of Science and Technology Beijing Beijing 100083 ChinaKey Laboratory of Advanced Materials and Devices for Post‐Moore Chips Ministry of Education School of Mathematics and Physics University of Science and Technology Beijing Beijing 100083 ChinaDepartment of Mechanical & Materials Engineering Portland State University Portland OR 97201 USAAbstract Crystals exhibiting glass‐like and low lattice thermal conductivity (κL) are not only scientifically intriguing but also practically valuable in various applications, including thermal barrier coatings, thermoelectric energy conversion, and thermal management. However, such unusual κL are typically observed only in compounds containing heavy elements, with large unit cells, or at high temperatures. In this study, chemical bonding principles are utilized to weaken the Ag–Ag bonds and enhance lattice anharmonicity. The incorporation of a chalcogen anion as a bridge ligand is proposed to facilitate phonon rattling in Ag6‐octahedron‐based compounds. Guided by this design strategy, five Ag6 octahedron‐based compounds, AAg3X2 (A = Li, Na, and K; X = S and Se), which are characterized by low average atomic masses and exhibit exceptionally strong four‐phonon scattering, are theoretically identified. Consequently, these compounds demonstrate ultralow thermal conductivities (0.3–0.6 W m−1 K−1) with minimal temperature dependence (T−0.1) across a wide temperature range. Experimental validation confirms that the κL of NaAg3S2 is 0.45 W m−1 K−1 within the temperature range of 200–550 K. The results clearly demonstrate that weak chemical bonding plays a crucial role in designing compounds with glass‐like κL, highlighting the effectiveness of chemical bonding engineering in achieving desired thermal transport properties.https://doi.org/10.1002/advs.202417292chemical bonding principleslattice thermal conductivitymaterial design and discoverysolid state chemistry
spellingShingle Zhonghao Xia
Xingchen Shen
Jun Zhou
Yuling Huang
Yali Yang
Jiangang He
Yi Xia
Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
Advanced Science
chemical bonding principles
lattice thermal conductivity
material design and discovery
solid state chemistry
title Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
title_full Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
title_fullStr Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
title_full_unstemmed Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
title_short Realizing Intrinsically Ultralow and Glass‐Like Thermal Transport via Chemical Bonding Engineering
title_sort realizing intrinsically ultralow and glass like thermal transport via chemical bonding engineering
topic chemical bonding principles
lattice thermal conductivity
material design and discovery
solid state chemistry
url https://doi.org/10.1002/advs.202417292
work_keys_str_mv AT zhonghaoxia realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT xingchenshen realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT junzhou realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT yulinghuang realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT yaliyang realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT jianganghe realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering
AT yixia realizingintrinsicallyultralowandglasslikethermaltransportviachemicalbondingengineering