Tunable thermal expansion in framework materials through redox intercalation.
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.
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Jun
J
Chen
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Qilong
Q
Gao
Department of Physics and Astronomy, University of Padova, I-35131 Padova, Italy.
Andrea
A
Sanson
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, Beijing 100190, China.
Xingxing
X
Jiang
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, USA.
Qingzhen
Q
Huang
Department of Physics and Astronomy, University of Padova, I-35131 Padova, Italy.
Alberto
A
Carnera
Elettra Sicrotrone Trieste, Strada Statale 14 - km, in AREA Science Park, 34149 Basovizza, Italy.
Clara Guglieri
CG
Rodriguez
Elettra Sicrotrone Trieste, Strada Statale 14 - km, in AREA Science Park, 34149 Basovizza, Italy.
Luca
0000-0002-8368-7105
L
Olivi
Center for Condensed Matter and Materials Physics, Department of Physics, Beihang University, Beijing 100191, China.
Lei
L
Wang
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Lei
L
Hu
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Kun
K
Lin
Argonne National Laboratory, X-Ray Science Division, Argonne, Illinois 60439, USA.
Yang
Y
Ren
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, Beijing 100190, China.
Zheshuai
Z
Lin
Center for Condensed Matter and Materials Physics, Department of Physics, Beihang University, Beijing 100191, China.
Cong
C
Wang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
Lin
L
Gu
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Jinxia
J
Deng
Centre for Science at Extreme Conditions and School of Chemistry, University of Edinburgh, Peter Guthrie Tait Road, King's Buildings, Edinburgh EH9 3FD, UK.
J Paul
0000-0001-9763-3987
JP
Attfield
Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Xianran
X
Xing