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

Abstract

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 NaHf 2P 3O 12 (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 Na 3Zr 2Si 2PO 12 (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 integrationmore » 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.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Sandia National Laboratories, Albuquerque, USA 87185
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Electricity Delivery and Energy Reliability (OE); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1510137
Alternate Identifier(s):
OSTI ID: 1437064; OSTI ID: 1485832
Report Number(s):
SAND-2018-13334J
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:  
NA0003525; AC04-94AL85000
Resource Type:
Published Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Name: Journal of Materials Chemistry. A Journal Volume: 6 Journal Issue: 20; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Small, Leo J., Wheeler, Jill S., Ihlefeld, Jon F., Clem, Paul G., and Spoerke, Erik D. Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor. United Kingdom: N. p., 2018. Web. doi:10.1039/C7TA09924J.
Small, Leo J., Wheeler, Jill S., Ihlefeld, Jon F., Clem, Paul G., & Spoerke, Erik D. Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor. United Kingdom. doi:10.1039/C7TA09924J.
Small, Leo J., Wheeler, Jill S., Ihlefeld, Jon F., Clem, Paul G., and Spoerke, Erik D. Tue . "Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor". United Kingdom. doi:10.1039/C7TA09924J.
@article{osti_1510137,
title = {Enhanced alkaline stability in a hafnium-substituted NaSICON ion conductor},
author = {Small, Leo J. and Wheeler, Jill S. and Ihlefeld, Jon F. and Clem, Paul G. and Spoerke, Erik D.},
abstractNote = {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.},
doi = {10.1039/C7TA09924J},
journal = {Journal of Materials Chemistry. A},
number = 20,
volume = 6,
place = {United Kingdom},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C7TA09924J

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1 : Log-scale X-ray (Cu Ka) diffraction patterns of (A) NHP and (B) NZP powders as-synthesized and after aging for 72 h at 80 °C in different aqueous 10 M NaOH or KOH. Asterisks (*) denote a slight HfP2O7 impurity. Red bars at the bottom of each plot denotemore » PDFs for (A) NHP (04-002-2743) and (B) NZP (01-071-0959). Black bars denote PDFs for (A) Hf)2 (04-001-7440) and (B) ZrO2 (04-002-8305).« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.