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Title: Crystal structure and elementary properties of Na{sub x}CoO{sub 2} (x=0.32, 0.51, 0.6, 0.75, and 0.92) in the three-layer NaCoO{sub 2} family

Abstract

The crystal structures of Na{sub x}CoO{sub 2} phases based on three-layer NaCoO{sub 2}, with x=0.32, 0.51, 0.60, 0.75, and 0.92, determined by powder neutron diffraction, are reported. The structures have triangular CoO{sub 2} layers interleaved by sodium ions, and evolve with variation in Na content in a more complex way than has been observed in the two-layer Na{sub x}CoO{sub 2} system. The phases with highest and lowest Na content studied (x=0.92 and 0.32) are trigonal, with three CoO{sub 2} layers per cell and octahedral Na ion coordination. The intermediate compositions have monoclinic structures. The x=0.75 compound has one CoO{sub 2} layer per cell, with Na in octahedral coordination and an incommensurate superlattice. The x=0.6 and 0.51 phases are also single layer, but the Na is found in trigonal prismatic coordination. The magnetic behavior of the phases is similar to that observed in the two-layer system. Both the susceptibility and the electronic contribution to the specific heat are largest for x=0.6.

Authors:
; ; ;  [1];  [2];  [3];  [1];  [4];  [5]; ;  [6]
  1. Department of Chemistry, Princeton University, Princeton, New Jersey 08540 (United States)
  2. National Centre for HREM, Department of Nanoscience, Delft Institute of Technology, Al Delft, The Netherlands (Netherlands)
  3. NIST Center for Neutron Research, NIST, Gaithersburg, Maryland 20899 (United States)
  4. (Japan)
  5. Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974 (United States)
  6. Department of Physics, Princeton University, Princeton, New Jersey 08540 (United States)
Publication Date:
OSTI Identifier:
20788155
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 73; Journal Issue: 17; Other Information: DOI: 10.1103/PhysRevB.73.174104; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; CONCENTRATION RATIO; LAYERS; MAGNETIC SUSCEPTIBILITY; MONOCLINIC LATTICES; NEUTRON DIFFRACTION; POWDERS; SODIUM COMPOUNDS; SODIUM IONS; SPECIFIC HEAT; SUPERLATTICES

Citation Formats

Viciu, L., Bos, J. W. G., Foo, M. L., Cava, R. J., Zandbergen, H. W., Huang, Q., Ishiwata, S., Department of Applied Physics, Waseda University, Ookubo, Shinjuku, Tokyo, 169-8555, Ramirez, A. P., Lee, M., and Ong, N. P. Crystal structure and elementary properties of Na{sub x}CoO{sub 2} (x=0.32, 0.51, 0.6, 0.75, and 0.92) in the three-layer NaCoO{sub 2} family. United States: N. p., 2006. Web. doi:10.1103/PHYSREVB.73.1.
Viciu, L., Bos, J. W. G., Foo, M. L., Cava, R. J., Zandbergen, H. W., Huang, Q., Ishiwata, S., Department of Applied Physics, Waseda University, Ookubo, Shinjuku, Tokyo, 169-8555, Ramirez, A. P., Lee, M., & Ong, N. P. Crystal structure and elementary properties of Na{sub x}CoO{sub 2} (x=0.32, 0.51, 0.6, 0.75, and 0.92) in the three-layer NaCoO{sub 2} family. United States. doi:10.1103/PHYSREVB.73.1.
Viciu, L., Bos, J. W. G., Foo, M. L., Cava, R. J., Zandbergen, H. W., Huang, Q., Ishiwata, S., Department of Applied Physics, Waseda University, Ookubo, Shinjuku, Tokyo, 169-8555, Ramirez, A. P., Lee, M., and Ong, N. P. Mon . "Crystal structure and elementary properties of Na{sub x}CoO{sub 2} (x=0.32, 0.51, 0.6, 0.75, and 0.92) in the three-layer NaCoO{sub 2} family". United States. doi:10.1103/PHYSREVB.73.1.
@article{osti_20788155,
title = {Crystal structure and elementary properties of Na{sub x}CoO{sub 2} (x=0.32, 0.51, 0.6, 0.75, and 0.92) in the three-layer NaCoO{sub 2} family},
author = {Viciu, L. and Bos, J. W. G. and Foo, M. L. and Cava, R. J. and Zandbergen, H. W. and Huang, Q. and Ishiwata, S. and Department of Applied Physics, Waseda University, Ookubo, Shinjuku, Tokyo, 169-8555 and Ramirez, A. P. and Lee, M. and Ong, N. P.},
abstractNote = {The crystal structures of Na{sub x}CoO{sub 2} phases based on three-layer NaCoO{sub 2}, with x=0.32, 0.51, 0.60, 0.75, and 0.92, determined by powder neutron diffraction, are reported. The structures have triangular CoO{sub 2} layers interleaved by sodium ions, and evolve with variation in Na content in a more complex way than has been observed in the two-layer Na{sub x}CoO{sub 2} system. The phases with highest and lowest Na content studied (x=0.92 and 0.32) are trigonal, with three CoO{sub 2} layers per cell and octahedral Na ion coordination. The intermediate compositions have monoclinic structures. The x=0.75 compound has one CoO{sub 2} layer per cell, with Na in octahedral coordination and an incommensurate superlattice. The x=0.6 and 0.51 phases are also single layer, but the Na is found in trigonal prismatic coordination. The magnetic behavior of the phases is similar to that observed in the two-layer system. Both the susceptibility and the electronic contribution to the specific heat are largest for x=0.6.},
doi = {10.1103/PHYSREVB.73.1},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 17,
volume = 73,
place = {United States},
year = {Mon May 01 00:00:00 EDT 2006},
month = {Mon May 01 00:00:00 EDT 2006}
}
  • Rare earth tin antimonides, RESn{sub x}Sb{sub 2} (RE = La, Ce, Pr, Nd, Sm) were synthesized by stoichiometric combination of the elements at high temperature. For the La compound, Sn content was varied from 0.1 {le} x {le} 0.8 and the crystal structure of x = 0.75 is reported. LaSn{sub 0.75}Sb{sub 2} crystallizes in the orthorhombic space group D{sup 17}{sub 2h}-Cmcm.
  • Ruddlesden–Popper n=2 member phases Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been investigated by X-ray and neutron powder diffraction, thermogravimetry and Mössbauer spectroscopy. Both samples as-prepared at 1300 °C under N{sub 2}(g) flow and samples subsequently air-annealed at 900 °C were studied. The as-prepared x=0.75 phase is highly oxygen deficient with δ=1, the O1 atom site being vacant, and the Fe{sup 3+}/Ni{sup 2+} ions having a square pyramidal coordination. For as-prepared phases with lower x values, the Mössbauer spectral data are in good agreement with the presence of both 5- and 4-coordinated Fe{sup 3+} ions, implying in addition amore » partial occupancy of the O3 atom sites that form the basal plane of the square pyramid. The air-annealed x=0.75 sample has a δ value of 0.61(1) and the structure has Fe/Ni ions in both square pyramids and octahedra. Mössbauer spectroscopy shows the phase to contain only Fe{sup 3+}, implying that all Ni is present as Ni{sup 3+}. Air-annealed phases with lower x values are found to contain both Fe{sup 3+} and Fe{sup 4+}. For both the as-prepared and the air-annealed samples, the Y{sup 3+} cations are found to be mainly located in the perovskite block. The high-temperature thermal expansion of as-prepared and air-annealed x=0.75 phases were investigated by high-temperature X-ray diffraction and dilatometry and the linear thermal expansion coefficient determined to be 14.4 ppm K{sup −1}. Electrical conductivity measurements showed that the air-annealed samples have higher conductivity than the as-prepared ones. - Highlights: • Ruddlesden–Popper, n=2, Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been synthesised. • The crystal structures of the phases have been determined. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6}, made in N{sub 2}(g) has Fe{sup 3+}/Ni{sup 2+} in square pyramides. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6.4}, made in air has Fe{sup 3+}/Ni{sup 3+} in square pyramides and octahedra. • Air annealed samples have higher electrical conductivity than N{sub 2}(g) annealed.« less
  • The syntheses, structures, and physical properties of several members of a new family of noncentrosymmetric, open-framework, ion-exchangeable phases which have a substantial nonlinear optical response (Nd:YAG 1064 nm) are described. Single-crystal (to 2 mm) hydrothermal synthesis of Na[sub 1/2](H[sub 3]O)[sub 1/2]Nb[sub 2]PO[sub 8] was carried out at 30,000-40,000 psi and 650-700[degrees]C. The structure of Na[sub 1/2](H[sub 3]O)[sub 1/2]Nb[sub 2]PO[sub 8], as determined from single-crystal X-ray data consists of an octahedral (NbO[sub 6])/tetrahedral (PO[sub 4]) framework, connected via Nb-O-P and Nb-O-Nb bonds, with cavities and channels occupied by the Na[sup +] and H[sub 3]O[sup +] cations. Members of the solid solutionmore » K[sub 2/3]Li[sub 1/3]Nb[sub 2[minus]x]Ta[sub x]PO[sub 8] (0 < x < 2) have been synthesized as powders by solid-state methods and are all isomorphous with Na[sub 1/2](H[sub 3]O)[sub 1/2]Nb[sub 2]PO[sub 8]. Various ion-exchange reactions with NH[sub 4][sup +], Rb[sup +], and Ag[sup +] are possible. These materials have been characterized by X-ray powder diffraction, TGA, [sup 31]P MAS NMR spectroscopy, second-harmonic generation measurements, and UV/visible spectroscopy. Crystal data: Na[sub 1/2](H[sub 3]O)[sub 1/2]Nb[sub 2]PO[sub 8], M[sub r] = 364.94, rhombohedral, R32 (No. 155), a = 8.4962 [angstrom], [alpha] = 104.775[degrees], V = 538.77 [angstrom][sup 3], Z = 3, R = 2.88%, R[sub w] = 3.56% for 66 parameters and 743 observations [I > 3[sigma](I)]. 23 refs., 10 figs., 5 tabs.« less
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