Tunable thermal expansion in framework materials through redox intercalation

Jun Chen, Qilong Gao, Andrea Sanson, Xingxing Jiang, Qingzhen Huang, Alberto Carnera, Clara Guglieri Rodriguez, Luca Olivi, Lei Wang, Lei Hu, Kun Lin, Yang Ren, Zheshuai Lin, Cong Wang, Lin Gu, Jinxia Deng, J. Paul Attfield () and Xianran Xing ()
Additional contact information
Jun Chen: University of Science and Technology Beijing
Qilong Gao: University of Science and Technology Beijing
Andrea Sanson: University of Padova
Xingxing Jiang: Center for Crystal R&D, Key Lab of Functional Crystals and Laser Technology of Chinese Academy of Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences
Qingzhen Huang: NIST Center for Neutron Research, National Institute of Standards and Technology
Alberto Carnera: University of Padova
Clara Guglieri Rodriguez: Elettra Sicrotrone Trieste, Strada Statale 14 - km, in AREA Science Park
Luca Olivi: Elettra Sicrotrone Trieste, Strada Statale 14 - km, in AREA Science Park
Lei Wang: Center for Condensed Matter and Materials Physics, Beihang University
Lei Hu: University of Science and Technology Beijing
Kun Lin: University of Science and Technology Beijing
Yang Ren: Argonne National Laboratory
Zheshuai Lin: Center for Crystal R&D, Key Lab of Functional Crystals and Laser Technology of Chinese Academy of Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences
Cong Wang: Center for Condensed Matter and Materials Physics, Beihang University
Lin Gu: Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences
Jinxia Deng: University of Science and Technology Beijing
J. Paul Attfield: Centre for Science at Extreme Conditions and School of Chemistry, University of Edinburgh, Peter Guthrie Tait Road, King’s Buildings
Xianran Xing: University of Science and Technology Beijing

Nature Communications, 2017, vol. 8, issue 1, 1-7

Abstract: 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. 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. 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.

Date: 2017
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DOI: 10.1038/ncomms14441

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