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Title: On the origin of high ionic conductivity in Na-doped SrSiO 3

Abstract

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation of an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclearmore » high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5];  [5];  [2]; ORCiD logo [6]
  1. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of South Carolina, Columbia, SC (United States). Dept. of Mechanical Engineering
  3. Florida State Univ., Tallahassee, FL (United States). Dept. of Scientific Computing
  4. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials
  5. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab). Centre of Interdisciplinary Magnetic Resonance
  6. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry; Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab). Centre of Interdisciplinary Magnetic Resonance
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); National Science Foundation (NSF)
OSTI Identifier:
1437305
Grant/Contract Number:  
AR0000492; 1508404
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Chien, Po-Hsiu, Jee, Youngseok, Huang, Chen, Dervi?o?lu, Riza, Hung, Ivan, Gan, Zhehong, Huang, Kevin, and Hu, Yan-Yan. On the origin of high ionic conductivity in Na-doped SrSiO3. United States: N. p., 2016. Web. doi:10.1039/c5sc04270d.
Chien, Po-Hsiu, Jee, Youngseok, Huang, Chen, Dervi?o?lu, Riza, Hung, Ivan, Gan, Zhehong, Huang, Kevin, & Hu, Yan-Yan. On the origin of high ionic conductivity in Na-doped SrSiO3. United States. doi:10.1039/c5sc04270d.
Chien, Po-Hsiu, Jee, Youngseok, Huang, Chen, Dervi?o?lu, Riza, Hung, Ivan, Gan, Zhehong, Huang, Kevin, and Hu, Yan-Yan. Wed . "On the origin of high ionic conductivity in Na-doped SrSiO3". United States. doi:10.1039/c5sc04270d. https://www.osti.gov/servlets/purl/1437305.
@article{osti_1437305,
title = {On the origin of high ionic conductivity in Na-doped SrSiO3},
author = {Chien, Po-Hsiu and Jee, Youngseok and Huang, Chen and Dervi?o?lu, Riza and Hung, Ivan and Gan, Zhehong and Huang, Kevin and Hu, Yan-Yan},
abstractNote = {Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO3 structure to form NaxSr1-xSiO3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation of an amorphous phase β-Na2Si2O5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na2Si2O5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.},
doi = {10.1039/c5sc04270d},
journal = {Chemical Science},
number = 6,
volume = 7,
place = {United States},
year = {2016},
month = {2}
}

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Cited by: 9 works
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Figures / Tables:

Fig. 1 Fig. 1: 29Si MAS NMR spectra of Na-doped SrSiO3 (with apparent composition of NaxSr1 xSiO3 0.5x) with different Na contents (x = 0, 0.1, 0.2, 0.3, 0.4, 0.45 and 0.70, denoted as SNS0, SNS10, SNS20, SNS30, SNS40, SNS45 and SNS70, respectively) and lab-synthesized $\beta$- Na2Si2O5. Relevant resonance assignments, including SrSiO3more » (red), SrSiO3 with Na doped within the structure (Sr(Na)SiO3, green), Na2SiO3 (magenta), and b-Na2Si2O5 (blue) are marked on the spectra. Spectral simulations are displayed together with the experimental spectra. All the NMR parameters used for the simulations are listed in Table S1.†« less

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