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Optimizing and Improving the Sodium Ion Conductivity of Nasicon

Monday, 30 May 2016: 14:00
Indigo Ballroom B (Hilton San Diego Bayfront)
A. G. Jolley, D. D. Taylor (University of Maryland Materials Science and Engineering), and E. D. Wachsman (University of Maryland Energy Research Center)
NASICON (Na3Zr2Si2PO12) has shown promise as a solid state electrolyte for a sodium battery due to its inherent safety and relatively high conductivity.  Increasing the conductivity of NASICON to further improve the capability of a solid state electrolyte has come by way aliovalent substitution of the zirconium site in Na3Zr2Si2PO12. Both Na3.2Zr1.8M0.2Si2PO12 (M=Al3+, Fe3+, Y3+) and Na3.4Zr1.8M0.2Si2PO12 (M=Co2+, Ni2+, Zn2+) have exhibited greater bulk conductivity at room temperature than undoped NASICON. A decrease in low temperature activation energy as well as the lowered rhombohedral-monoclinic phase transformation temperature is responsible for the increased bulk conductivity of substituted NASICON.  The Co, Zn, and Ni dopants were explored more extensively as they displayed the highest conductivity of 10% doped NASICON at room temperature. By adjusting the total substitution of Co, Zn, and Ni cations, the conductivity of NASICON was optimized further. Increasing the amount of Zn+2 dopant in Na3+2xZr2-xZnxSi2PO12 resulted in reduced distortion of the lattice as it transitioned from rhombohedral to monoclinic phase, and an increase in conductivity. Ultimately the bulk ionic conductivity of 20% Zn-doped NASICON is among the highest ever reported.