Chemistry:Sodium cobalt oxide
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| Other names
sodium cobaltate
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| Identifiers | |
3D model (JSmol)
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| Properties | |
| CoNaO2 | |
| Molar mass | 113.921 g·mol−1 |
| Density | 4.95 g·cm−3[1] |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
Sodium cobalt oxide, also called sodium cobaltate, is any of a range of compounds of sodium, cobalt, and oxygen with the general formula NaxCoO2 for 0 < x ≤ 1. The name is also used for hydrated forms of those compounds, NaxCoO2·yH2O.
The anhydrous compound was first synthesized in the 1970s.[2] It conducts like a metal, and has exceptional thermoelectric properties (for 0.5 ≤ x ≤ 0.75) combining a large Seebeck coefficient with low resistivity, as discovered in 1997 by Ichiro Terasaki's research group.[2] A hydrate form was found to be superconducting below 5 K.[2] The compound, and its manganese analog, could be a cheaper alternative to the analogous lithium compounds.[3]
Structure
Like other alkali-cobalt oxides, sodium cobaltate has a layer structure. Layers of monovalent sodium cations (Na+) alternate with two-dimensional anionic sheets of cobalt and oxygen atoms. Each cobalt atom is bound to six oxygen atoms forming an octahedron, with two faces parallel to the layer plane. The octahedra share edges, resulting in a layer of cobalt atoms sandwiched between two layers of oxygen atoms, all three with regular triangular roughly planar lattice .[2] The structure is reminiscent of cuprate superconductors, except that the copper atom arrangement in the latter is a square lattice.[2]
The cobalt atoms have formal oxidation state 4−x. Namely, the fully reduced compound NaCoO2 can be interpreted as Na+·Co3+·(O2−)2. As the compound is oxidized, sodium cations exit the structure and the cobalt formally approaches the Co4+ state.
For x above 0.5, the sodium ions adopt many different arrangements in which Na ions occupy two inequivalent Wyckoff sites, 2b and 2d, of the space group P63/mmc. In galvanostatic experiments, the arrangements transition at specific values of x as the sodium content is electrolytically varied. The diffusion rate of the ions, plotted as a function of x, shows sharp dips (from about 10−7 to 10−10 cm2/s at ambient temperature) at values of x that correspond to particular regular arrangements, namely 1/3, 1/2, and 5/7. Smaller and broader dips are observed around some other simple ratios, like 5/9.[3]
For x = 0.8, at 100 K the vacancies in the sodium layer are arranged in clusters of three. The clusters are arranged in stripes, with a fixed offset between the clusters in adjacent stripes. In those conditions, the diffusion rate of the sodium atoms is minimal. At about 290 K, the structure becomes partially disordered, with the offset of between adjacent stripes becoming random. creating channels that allow their quasi-unidimensional diffusion. The sodium lattice "melts" at about 370 K, allowing two-dimensional diffusion.[3]
As x increases, the conductivity along the main crystal planes increases, until about x = 0.85, and is roughly independent of x thereafter. The temperature dependency at those higher concentrations has metallic character. The thermopower S increases with x up to 0.97, but drops for higher x. For each composition, as a function of temperature it increases rapidly until about 130 K, and then decreases gradually. The figure of merit Z = S/ρκ (where ρ is the in-plane resistivity and κ is the thermal conductivity) is maximum for x about 0.89 at about 65 K.[4]
Preparation
The fully reduced compound NaCoO2 can be prepared by dissolving stoichiometric amounts of sodium acetate C2H3O2Na and cobalt tartrate C4H4O6Co in ethanol with a gelling agent, drying and calcinating the resulting gel, and annealing it at 650 °C.[5]
The compound Na0.5CoO2 (or NaCo2O4) can be obtained in the form of platelets up to 6 mm wide from metallic cobalt powder, by treatment with molten sodium chloride and sodium hydroxide at 550 °C.[6]
The compound NaxCoO2 with x around 0.8 can be obtained by treating a mixture of sodium carbonate Na2CO3 and cobalt(II,III) oxide Co3O4 at 850–1050 °C.[7] Single crystals of Na0.8CoO2 can be grown by the optical floating-zone technique.[3]
Higher values of x can be obtained by immersing thermally grown crystals of Na0.71CoO2 in a hot solution prepared from sodium metal and benzophenone in tetrahydrofuran for several days at 100 C.[4]
See also
References
- ↑ Jansen, M.; Hoppe, R. Oxocobaltates of sodium. Zeitschrift fuer Anorganische und Allgemeine Chemie, 1974. 408 (2): 104-106. ISSN 0044-2313.
- ↑ 2.0 2.1 2.2 2.3 2.4 Barbara Goss Levi (2003), "Intriguing Properties Put Sodium Cobalt Oxide in the Spotlight". Physics Today, volume 56, issue 8, page 15. doi:10.1063/1.1611341
- ↑ 3.0 3.1 3.2 3.3 T. J. Willis, D. G. Porter, D. J. Voneshen, S. Uthayakumar, F Demmel, M. J. Gutmann, K. Refson, and J. P. Goff (2018) "Diffusion mechanism in the sodium-ion battery material sodium cobaltate". Scientific Reports, volume 8, report 3210. doi:10.1038/s41598-018-21354-5
- ↑ 4.0 4.1 Minhyea Lee, Liliana Viciu, Luli Yayuwang, M. L. Foo, S. Watauchi, R. A. Pascal Jr., R. J. Cava, and N. P. Ong (2006): "Large enhancement of the thermopower in NaxCoO2 at high Na doping". Nature Materials Letters, volume 6, pages 537–540, doi:10.1038/nmat1669
- ↑ Nur Khairani Samin, Roshidah Rusdi, Norashikin Kamarudin, and Norlida Kamarulzaman (2012), "Synthesis and Battery Studies of Sodium Cobalt Oxides, NaCoO2". Advanced Materials Research, volume 545, pages 185–189. doi:10.4028/www.scientific.net/AMR.545.185
- ↑ Xiaofeng Tang (2005), "Synthesis and properties of sodium cobalt oxide thermoelectric materials". Research Gate, accessed on 2018-04-09.
- ↑ I. F. Gilmutdinov, I. R. Mukhamedshin, F. Rullier-Albenque, H. Alloul (2017), "Synthesis of sodium cobaltate NaxCoO2 single crystals with controlled Na ordering]". arXiv:1711.01611
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