Tunable thermal expansion in framework materials through redox intercalation

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

doi:10.1038/ncomms14441

Title: Tunable thermal expansion in framework materials through redox intercalation

Journal Article · 08 February 2017 · Nature Communications

DOI: https://doi.org/10.1038/ncomms14441 · OSTI ID:1367161

Chen, Jun ^[1]; Gao, Qilong ^[1]; Sanson, Andrea ^[2]; Jiang, Xingxing ^[3]; Huang, Qingzhen ^[4]; Carnera, Alberto ^[2]; Rodriguez, Clara Guglieri ^[5];

^[5]; Wang, Lei ^[6]; Hu, Lei ^[1]; Lin, Kun ^[1]; Ren, Yang ^[7]; Lin, Zheshuai ^[3]; Wang, Cong ^[6]; Gu, Lin ^[3]; Deng, Jinxia ^[1];

^[8]; Xing, Xianran ^[1]

Univ. of Science and Technology Beijing, Beijing (China)
Univ. of Padova, Padova (Italy)
Chinese Academy of Sciences (CAS), Beijing (China)
National Institute of Standards and Technology, Gaithersburg, MD (United States)
Elettra Sicrotrone Trieste, Basovizza (Italy)
Beihang Univ., Beijing (China)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Edinburgh, Edinburgh (United Kingdom)

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.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1367161

Journal Information:: Nature Communications, Journal Name: Nature Communications Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Tunable thermal expansion in framework materials through redox intercalation

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