Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor

Small, Leo J.; Wheeler, Jill S.; Ihlefeld, Jon F.; Clem, Paul G.; Spoerke, Erik David

doi:10.1039/C7TA09924J

Title: Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor

Journal Article · 14 May 2018 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/C7TA09924J · OSTI ID:1510137

^[1]; Wheeler, Jill S. ^[1];

^[1]; Clem, Paul G. ^[1];

^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

In this paper, we present a multi-length scale integration of compositionally tailored NaSICON-based Na⁺ conductors to create a high Na⁺ conductivity system resistant to chemical attack in strongly alkaline aqueous environments. Using the Pourbaix Atlas as a generalized guide to chemical stability, we identify NaHf₂P₃O₁₂ (NHP) as a candidate NaSICON material for enhanced chemical stability at pH > 12, and demonstrate the stability of NHP powders under accelerated aging conditions of 80 °C and pH = 13–15 for a variety of alkali metal cations. To compensate for the relatively low ionic conductivity of NHP, we develop a new low temperature (775 °C) alkoxide-based solution deposition chemistry to apply dense NHP thin films onto both platinized silicon wafers and bulk, high Na⁺ conductivity Na₃Zr₂Si₂PO₁₂ (NZSP) pellets. These NHP films display Na+ conductivities of 1.35 × 10^-5 S cm^-1 at 200 °C and an activation energy of 0.53 eV, similar to literature reports for bulk NHP pellets. Under aggressive conditions of 10 M KOH at 80 °C, NHP thin films successfully served as an alkaline-resistant barrier, extending the lifetime of NZSP pellets from 4.26 to 36.0 h. Lastlyl, this integration of compositionally distinct Na⁺ conductors across disparate length scales (nm, mm) and processing techniques (chemically-derived, traditional powder) represents a promising new avenue by which Na⁺ conducting systems may be utilized in alkaline environments previously thought incompatible with ceramic Na⁺ conductors.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Electricity (OE); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1510137

Alternate ID(s):: OSTI ID: 1437064; OSTI ID: 1485832

Report Number(s):: SAND-2018-13334J; JMCAET; 670303

Journal Information:: Journal of Materials Chemistry. A, Vol. 6, Issue 20; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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