Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces

M. A. Frechero, M. Rocci, G. Sanchez-Santolino, Amit Kumar, J. Salafranca, Rainer Schmidt, M. R. Diaz-Guillen, O. J. Dura, A Rivera-Calzada, R. Mishra, Stephen Jesse, S. T. Pantideles, Sergei V. Kalinin, Maria Varela, S. J. Pennycook, J. Santamaria, C. Leon

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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. Ultimately, it is this negative charge which gives rise to the barrier for ion transport at the grain boundary
Original languageEnglish
Article number17229
Number of pages23
JournalNature Scientific Reports
Volume5
DOIs
Publication statusPublished - 17 Dec 2015

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    Frechero, M. A., Rocci, M., Sanchez-Santolino, G., Kumar, A., Salafranca, J., Schmidt, R., Diaz-Guillen, M. R., Dura, O. J., Rivera-Calzada, A., Mishra, R., Jesse, S., Pantideles, S. T., Kalinin, S. V., Varela, M., Pennycook, S. J., Santamaria, J., & Leon, C. (2015). Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces. Nature Scientific Reports, 5, [17229 ]. https://doi.org/10.1038/srep17229