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Title: Tunable thermal expansion in framework materials through redox intercalation

Abstract

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

Authors:
 [1];  [1];  [2];  [3];  [4];  [2];  [5]; ORCiD logo [5];  [6];  [1];  [1];  [7];  [3];  [6];  [3];  [1]; ORCiD logo [8];  [1]
  1. Univ. of Science and Technology Beijing, Beijing (China)
  2. Univ. of Padova, Padova (Italy)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
  4. National Institute of Standards and Technology, Gaithersburg, MD (United States)
  5. Elettra Sicrotrone Trieste, Basovizza (Italy)
  6. Beihang Univ., Beijing (China)
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
  8. Univ. of Edinburgh, Edinburgh (United Kingdom)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
OSTI Identifier:
1367161
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; materials chemistry; solid-state chemistry

Citation Formats

Chen, Jun, Gao, Qilong, Sanson, Andrea, Jiang, Xingxing, Huang, Qingzhen, Carnera, Alberto, Rodriguez, Clara Guglieri, Olivi, Luca, Wang, Lei, Hu, Lei, Lin, Kun, Ren, Yang, Lin, Zheshuai, Wang, Cong, Gu, Lin, Deng, Jinxia, Attfield, J. Paul, and Xing, Xianran. Tunable thermal expansion in framework materials through redox intercalation. United States: N. p., 2017. Web. https://doi.org/10.1038/ncomms14441.
Chen, Jun, Gao, Qilong, Sanson, Andrea, Jiang, Xingxing, Huang, Qingzhen, Carnera, Alberto, Rodriguez, Clara Guglieri, Olivi, Luca, Wang, Lei, Hu, Lei, Lin, Kun, Ren, Yang, Lin, Zheshuai, Wang, Cong, Gu, Lin, Deng, Jinxia, Attfield, J. Paul, & Xing, Xianran. Tunable thermal expansion in framework materials through redox intercalation. United States. https://doi.org/10.1038/ncomms14441
Chen, Jun, Gao, Qilong, Sanson, Andrea, Jiang, Xingxing, Huang, Qingzhen, Carnera, Alberto, Rodriguez, Clara Guglieri, Olivi, Luca, Wang, Lei, Hu, Lei, Lin, Kun, Ren, Yang, Lin, Zheshuai, Wang, Cong, Gu, Lin, Deng, Jinxia, Attfield, J. Paul, and Xing, Xianran. Thu . "Tunable thermal expansion in framework materials through redox intercalation". United States. https://doi.org/10.1038/ncomms14441. https://www.osti.gov/servlets/purl/1367161.
@article{osti_1367161,
title = {Tunable thermal expansion in framework materials through redox intercalation},
author = {Chen, Jun and Gao, Qilong and Sanson, Andrea and Jiang, Xingxing and Huang, Qingzhen and Carnera, Alberto and Rodriguez, Clara Guglieri and Olivi, Luca and Wang, Lei and Hu, Lei and Lin, Kun and Ren, Yang and Lin, Zheshuai and Wang, Cong and Gu, Lin and Deng, Jinxia and Attfield, J. Paul and Xing, Xianran},
abstractNote = {Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.},
doi = {10.1038/ncomms14441},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}

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