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How to speed up ion transport in nanopores
Electrolyte-filled subnanometre pores exhibit exciting physics and play an increasingly important role in science and technology. In supercapacitors, for instance, ultranarrow pores provide excellent capacitive characteristics. However, ions experience difficulties in entering and leaving such pores, which slows down charging and discharging processes. In an earlier work we showed for a simple model that a slow voltage sweep charges ultranarrow pores quicker than an abrupt voltage step. A slowly applied voltage avoids ionic clogging and co-ion trapping—a problem known to occur when the applied potential is varied too quickly—causing sluggish dynamics. Herein, we verify this finding experimentally. Guided by theoretical considerations, we also develop a non-linear voltage sweep and demonstrate, with molecular dynamics simulations, that it can charge a nanopore even faster than the corresponding optimized linear sweep. For discharging we find, with simulations and in experiments, that if we reverse the applied potential and then sweep it to zero, the pores lose their charge much quicker than they do for a short-circuited discharge over their internal resistance. Our findings open up opportunities to greatly accelerate charging and discharging of subnanometre pores without compromising the capacitive characteristics, improving their importance for energy storage, capacitive deionization, and electrochemical heat harvesting.
Rocket measurements of positive ions during polar mesosphere winter echo conditions
On 18 January 2005, two small, instrumented rockets were launched from Andøya Rocket Range (69.3° N, 16° E) during conditions with Polar Mesosphere Winter Echoes (PMWE). Each of the rockets was equipped with a Positive Ion Probe (PIP) and a Faraday rotation/differential absorption experiment, and was launched as part of a salvo of meteorological rockets measuring temperature and wind using falling spheres and chaff. Layers of PMWE were detected between 55 and 77 km by the 53.5 MHz ALWIN radar. The rockets were launched during a solar proton event, and measured extremely high ion densities, of order 1010 m−3, in the region where PMWE were observed. The density measurements were analyzed with the wavelet transform technique. At large length scales, ~103 m, the power spectral density can be fitted with a k−3 wave number dependence, consistent with saturated gravity waves. Outside the PMWE layers the k−3 spectrum extends down to approximately 102 m where the fluctuations are quickly damped and disappear into the instrumental noise. Inside the PMWE layers the spectrum at smaller length scales is well fitted with a k−5/3 dependence over two decades of scales. The PMWE are therefore clearly indicative of turbulence, and the data are consistent with the turbulent dissipation of breaking gravity waves. We estimate a lower limit for the turbulent energy dissipation rate of about 10−2 W/kg in the upper (72 km) layer.
On the Dynamical Regimes of Pattern-Accelerated Electroconvection
Recent research has established that electroconvection can enhance ion transport at polarized surfaces such as membranes and electrodes where it would otherwise be limited by diffusion. The onset of such overlimiting transport can be influenced by the surface topology of the ion selective membranes as well as inhomogeneities in their electrochemical properties. However, there is little knowledge regarding the mechanisms through which these surface variations promote transport. We use high-resolution direct numerical simulations to develop a comprehensive analysis of electroconvective flows generated by geometric patterns of impermeable stripes and investigate their potential to regularize electrokinetic instabilities. Counterintuitively, we find that reducing the permeable area of an ion exchange membrane, with appropriate patterning, increases the overall ion transport rate by up to 80%. In addition, we present analysis of nonpatterned membranes and find a novel regime of electroconvection where a multivalued current is possible due to the coexistence of multiple convective states.