Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces
Abstract
The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. In conclusion, besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grainmore »
- Authors:
-
- Univ. Complutense de Madrid, Madrid (Spain); Univ. Nacional del Sur, Bahia Blanca, (Argentina)
- Univ. Complutense de Madrid, Madrid (Spain)
- Univ. Complutense de Madrid, Madrid (Spain); Materials Science & Technology Div., Oak Ridge, TN (United States)
- Center for Nanophase Materials Sciences, Oak Ridge, TN (United States)
- Materials Science & Technology Div., Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
- The Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1259714
- Grant/Contract Number:
- MAT2011-27470-C01; S2009/MAT-1756; 239739
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 5; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; fuel cells; surfaces, interfaces and thin films
Citation Formats
Frechero, M. A., Rocci, M., Sanchez-Santolino, G., Kumar, Amit, Salafranca, J., Schmidt, Rainer, Diaz-Guillen, M. R., Dura, O. J., Rivera-Calzada, A., Mishra, R., Jesse, Stephen, Pantelides, S. T., Kalinin, Sergei V., Varela, M., Pennycook, S. J., Santamaria, J., and Leon, C. Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces. United States: N. p., 2015.
Web. doi:10.1038/srep17229.
Frechero, M. A., Rocci, M., Sanchez-Santolino, G., Kumar, Amit, Salafranca, J., Schmidt, Rainer, Diaz-Guillen, M. R., Dura, O. J., Rivera-Calzada, A., Mishra, R., Jesse, Stephen, Pantelides, S. T., Kalinin, Sergei V., Varela, M., Pennycook, S. J., Santamaria, J., & Leon, C. Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces. United States. https://doi.org/10.1038/srep17229
Frechero, M. A., Rocci, M., Sanchez-Santolino, G., Kumar, Amit, Salafranca, J., Schmidt, Rainer, Diaz-Guillen, M. R., Dura, O. J., Rivera-Calzada, A., Mishra, R., Jesse, Stephen, Pantelides, S. T., Kalinin, Sergei V., Varela, M., Pennycook, S. J., Santamaria, J., and Leon, C. Thu .
"Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces". United States. https://doi.org/10.1038/srep17229. https://www.osti.gov/servlets/purl/1259714.
@article{osti_1259714,
title = {Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces},
author = {Frechero, M. A. and Rocci, M. and Sanchez-Santolino, G. and Kumar, Amit and Salafranca, J. and Schmidt, Rainer and Diaz-Guillen, M. R. and Dura, O. J. and Rivera-Calzada, A. and Mishra, R. and Jesse, Stephen and Pantelides, S. T. and Kalinin, Sergei V. and Varela, M. and Pennycook, S. J. and Santamaria, J. and Leon, C.},
abstractNote = {The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. In conclusion, besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.},
doi = {10.1038/srep17229},
journal = {Scientific Reports},
number = ,
volume = 5,
place = {United States},
year = {Thu Dec 17 00:00:00 EST 2015},
month = {Thu Dec 17 00:00:00 EST 2015}
}
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