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Improving the ionic conductivity of NASICON through aliovalent cation substitution of Na3Zr2Si2PO12

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Abstract

Doping the zirconium site in NASICON (Na3Zr2Si2PO12) with lower valent cations enhanced the ionic transport of the material. Both Na3.2Zr1.8M0.2Si2PO12 (M=Al3+, Fe3+, Y3+) and Na3.4Zr1.8M0.2Si2PO12 (M=Co2+, Ni2+, Zn2+) exhibited a higher bulk conductivity than undoped Na3Zr2Si2PO12 at room temperature. A decrease in the low temperature activation energy for all doped NASICON was observed, which helped contribute to the higher room temperature conductivity. The lower activation energy and enhanced conductivity of doped materials were a result of alterations in the NASICON structure. The charge imbalance created by aliovalent substitution increased the sodium in the lattice resulting in more charge carriers with better mobility. Furthermore, the conductivity was optimized by the ionic radius of the species in the zirconium site. Ultimately, NASICON doped with a +2 oxidation state cation having an ionic radius of approximately 0.73 Å (Zn and Co) attained a maximum in conductivity. Zn-doped NASICON displayed the greatest room temperature bulk conductivity of 3.75 × 10−3 S/cm, while Co-doped NASICON demonstrated the greatest total conductivity of 1.55 × 10−3 S/cm.

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Acknowledgments

We would like to acknowledge the support of the US Department of Energy’s Office of Electricity Delivery and Energy Reliability and Sandia National Laboratories, contract # 1161548, for the financial support, Phil Piccoli for his operation of the electron probe microanalyzer, and the University of Maryland NISPLab for providing access to microprobe.

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  1. University of Maryland Energy Research Center, University of Maryland, College Park, MD, 20742, USA

    Adam G. Jolley, Gil Cohn, Gregory T. Hitz & Eric D. Wachsman

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  1. Adam G. Jolley
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  2. Gil Cohn
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  4. Eric D. Wachsman
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Correspondence to Eric D. Wachsman.

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Jolley, A.G., Cohn, G., Hitz, G.T. et al. Improving the ionic conductivity of NASICON through aliovalent cation substitution of Na3Zr2Si2PO12 . Ionics 21, 3031–3038 (2015). https://doi.org/10.1007/s11581-015-1498-8

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  • DOI: https://doi.org/10.1007/s11581-015-1498-8

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