NASICON

2×2 unit cell of Na3Zr2(SiO4)2(PO4) (x = 2), which is the most common NASICON material;[1] red: O, purple: Na, light green: Zr, dark green: sites shared by Si and P
One unit cell of Na2Zr2(SiO4)(PO4)2 (x = 1); red: O, purple: Na, light green: Zr, dark green: sites shared by Si and P

NASICON is an acronym for sodium (Na) Super Ionic CONductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3-xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.[2]

Properties

The crystal structure of NASICON compounds was characterized in 1968. It is a covalent network consisting of ZrO6 octahedra and PO4/SiO4 tetrahedra that share common corners. Sodium ions are located at two types of interstitial positions. They move among those sites through bottlenecks, whose size, and thus the NASICON electrical conductivity, depends on the NASICON composition, on the site occupancy,[3] and on the oxygen content in the surrounding atmosphere. The conductivity decreases for x < 2 or when all Si is substituted for P in the crystal lattice (and vice versa); it can be increased by adding a rare-earth compound to NASICON, such as yttria.[1]

NASICON materials can be prepared as single crystals, polycrystalline ceramic compacts, thin films or as a bulk glass called NASIGLAS. Most of them, except NASIGLAS and phosphorus-free Na4Zr2Si3O12, react with molten sodium at 300 °C, and therefore are unsuitable for electric batteries that use sodium as an electrode.[2] However, a NASICON membrane is being considered for a sodium-sulfur battery where the sodium stays solid.

Potential applications

The main application envisaged for NASICON materials is as the solid electrolyte in a sodium-ion battery. Some NASICONs exhibit a low thermal expansion coefficient (< 10−6 K−1), which is useful for precision instruments and household ovenware. NASICONs can be doped with rare-earth elements, such as Eu, and used as phosphors. Their electrical conductivity is sensitive to molecules in the ambient atmosphere, a phenomenon that can be used to detect CO2, SO2, NO, NO2, NH3 and H2S gases. Other NASICON applications include catalysis, immobilization of radioactive waste, and sodium removal from water.[2]

References

  1. 1 2 Fergus, J. W. (2012). "Ion transport in sodium ion conducting solid electrolytes". Solid State Ionics 227: 102. doi:10.1016/j.ssi.2012.09.019.
  2. 1 2 3 Anantharamulu, N.; Koteswara Rao, K.; Rambabu, G.; Vijaya Kumar, B.; Radha, V.; Vithal, M. (2011). "A wide-ranging review on Nasicon type materials". Journal of Materials Science 46 (9): 2821. doi:10.1007/s10853-011-5302-5.
  3. ↑ Knauth, P. (2009). "Inorganic solid Li ion conductors: An overview". Solid State Ionics 180 (14–16): 911. doi:10.1016/j.ssi.2009.03.022.
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