TY - JOUR
T1 - LiIn2SbO6
T2 - A New Rutile-Related Structure Type with Unique Ion Channels
AU - Flynn, Steven
AU - Sanghvi, Sheel
AU - Nisbet, Matthew L.
AU - Griffith, Kent J.
AU - Zhang, Weiguo
AU - Halasyamani, P. Shiv
AU - Haile, Sossina M.
AU - Poeppelmeier, Kenneth R.
N1 - Funding Information:
The authors would like to thank Christos Malliakas, Zach Mansley, and Charlotte Stern for helpful discussions. This work was supported by the National Science Foundation (DMR-1720139 and DMR-1904701). This work made use of the IMSERC X-ray Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN); and the Jerome B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). Diffuse reflectance was collected at the NU Keck Biophysics Facility. P.S.H. and W.Z. thank the Welch Foundation (Grant E-1457) for support. K.J.G. acknowledges the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, and Basic Energy Sciences.
PY - 2020/6/9
Y1 - 2020/6/9
N2 - Single crystals of LiIn2SbO6 (LIAO) have been synthesized using a Li2MoO4 flux and characterized with X-ray diffraction. The compound crystallizes in a new structure type with a rutile-related framework. Like others in the rutile-related family, LIAO is formed of chains of edge-sharing octahedra. The chain structure, with a width that alternates between single and double octahedra, has not previously been reported in a rutile-related material. The framework is formed via corner sharing by the chains in a checkerboard arrangement, with Li+ residing in tetrahedral sites in the resulting, identically-alternating channels. Solid-state 6/7Li NMR spectroscopy and ab initio spectral calculations verify the presence of tetrahedrally coordinated lithium. The solution determined here contradicts previous reports of this material as a cation-ordered variant of LiSbO3. The relationship between this new structure and LiSbO3 and others in the rutile-related family is discussed. Variable temperature powder X-ray diffraction and diffuse reflectance show that LIAO has high thermal stability and a large direct band gap of 3.9 eV. AC impedance spectroscopy reveals that LIAO is a relatively poor Li conductor, displaying a conductivity of 1.3 × 10-7 S/cm at 623 K, along with an activation energy for charge transport of 1.1 eV. This material presents an opportunity to explore a new subfamily of rutile-related materials in which alternating-width chains may provide an independent avenue for tuning desired properties.
AB - Single crystals of LiIn2SbO6 (LIAO) have been synthesized using a Li2MoO4 flux and characterized with X-ray diffraction. The compound crystallizes in a new structure type with a rutile-related framework. Like others in the rutile-related family, LIAO is formed of chains of edge-sharing octahedra. The chain structure, with a width that alternates between single and double octahedra, has not previously been reported in a rutile-related material. The framework is formed via corner sharing by the chains in a checkerboard arrangement, with Li+ residing in tetrahedral sites in the resulting, identically-alternating channels. Solid-state 6/7Li NMR spectroscopy and ab initio spectral calculations verify the presence of tetrahedrally coordinated lithium. The solution determined here contradicts previous reports of this material as a cation-ordered variant of LiSbO3. The relationship between this new structure and LiSbO3 and others in the rutile-related family is discussed. Variable temperature powder X-ray diffraction and diffuse reflectance show that LIAO has high thermal stability and a large direct band gap of 3.9 eV. AC impedance spectroscopy reveals that LIAO is a relatively poor Li conductor, displaying a conductivity of 1.3 × 10-7 S/cm at 623 K, along with an activation energy for charge transport of 1.1 eV. This material presents an opportunity to explore a new subfamily of rutile-related materials in which alternating-width chains may provide an independent avenue for tuning desired properties.
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U2 - 10.1021/acs.chemmater.0c01491
DO - 10.1021/acs.chemmater.0c01491
M3 - Article
AN - SCOPUS:85088390211
VL - 32
SP - 4785
EP - 4794
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 11
ER -