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

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

Long-term changes in oxygen depletion in a small temperate lake: effects of climate change and eutrophication

1. We analysed 41 years of data (1968–2008) from Blelham Tarn, U.K., to determine the consequences of eutrophication and climate warming on hypolimnetic dissolved oxygen (DO).
2. The establishment of thermal stratification was strongly related to the onset of DO depletion in the lower hypolimnion. As a result of a progressively earlier onset of stratification and later overturn, the duration of stratification increased by 38 ± 8 days over the 41 years.
3. The observed rate of volumetric hypolimnetic oxygen depletion (VHODobs) ranged from 0.131 to 0.252 g O2 m−3 per day and decreased significantly over the study period, despite the increase in the mean chlorophyll a (Chl a) concentration in the growing season. The vertical transport of DO represented from 0 to 30% of VHODobs, while adjustments for interannual differences in hypolimnetic temperature were less important, ranging from −11 to 9% of VHODobs.
4. The mean wind speed during May made the strongest significant contribution to the variation in VHODobs. VHODobs adjusted for the vertical transport of DO and hypolimnetic temperature differences, VHODadj, was significantly related to the upper mixed layer Chl a concentration during spring.
5. Hypolimnetic anoxia (HA) ranged from 27 to 168 days per year and increased significantly over time, which undoubtedly had negative ecological consequences for the lake.
6. In similar small temperate lakes, the negative effects of eutrophication on hypolimnetic DO are likely to be exacerbated by changes in lake thermal structure brought about by a warming climate, which may undermine management efforts to alleviate the effects of anthropogenic eutrophication.