The ''capacitive mixing'' (CAPMIX) technique is aimed at the extraction of energy from the salinity difference between the sea and rivers. It is based on the voltage rise that takes place at the electrodes when changing the salt concentration of the solution in which the two electrodes are dipped. In this paper, we focus on activated carbon electrodes, produced with various methods and treatments, and we measure their behaviour in CAPMIX experiments. We find that they behave as polarizable electrodes only on time scales of the order of minutes, while on longer time scales they tend to move to a specific ''spontaneous'' potential, likely due to chemical redox reactions. This analysis sheds light on the charge leakage, i.e. the loss of the stored charge due to undesired chemical reactions, which is one of the main hurdles of the CAPMIX technique when performed with activated carbon electrodes. We show that the leakage finds its origin in the tendency of the electrode to move to its spontaneous potential. Our investigation allows us to completely get rid of the leakage and demonstrates the striking result that CAPMIX cycles can be performed without an external power supply.
An enormous dissipation of the order of 2 kJ/L takes place during the natural mixing process of fresh river water entering the salty sea. "Capacitive mixing" is a promising technique to efficiently harvest this energy in an environmentally clean and sustainable fashion. This method has its roots in the ability to store a very large amount of electric charge inside supercapacitor or battery electrodes dipped in a saline solution. Three different schemes have been studied so far, namely, Capacitive Double Layer Expansion (CDLE), Capacitive Donnan Potential (CDP) and Mixing Entropy Battery (MEB), respectively based on the variation upon salinity change of the electric double layer capacity, on the Donnan membrane potential, and on the electrochemical energy of intercalated ions.
Electrochemical cells containing two electrodes dipped in an ionic solution are widely used as charge accumulators, either with polarizable (supercapacitor) or nonpolarizable (battery) electrodes. Recent applications include desalination ("capacitive deionization") and energy extraction from salinity differences ("capacitive mixing"). In this Letter, we analyze a general relation between the variation of the electric potential as a function of the concentration and the salt adsorption. This relation comes from the evaluation of the electrical and mechanical energy exchange along a reversible cycle, which involves salt adsorption and release by the electrodes. The obtained relation thus describes a connection between capacitive deionization and capacitive mixing. We check this relation with experimental data already reported in the literature, and moreover by some classical physical models for electrodes, including polarizable and nonpolarizable electrodes. The generality of the relation makes it very useful in the study of the properties of the electric double layer.
A model of the electro-diffusion of ions in porous electrodes
is
applied to analyze the dynamics of capacitive-mixing extraction of
energy from salinity gradients with carbon porous electrodes. The
complex time-evolution of the cell voltage observed in experiments
is satisfactorily described. The asymmetry on the duration of the
solution-change steps performed in open circuit is found to be due
to the nonlinear voltage–concentration relationship of the
electric double layers and to a current that redistributes the counterions
along the depth of the electrode leading to nonuniform charge and
salt adsorption. The validated model is an essential tool for the
design and optimization of renewable energy extraction by this technique.
The opening of DNA double strands is extremely relevant to several biological functions, such as replication and transcription or binding of specific proteins. Such opening phenomenon is particularly sensitive to the aqueous solvent conditions in which the DNA molecule is dispersed, as it can be observed by considering the classical dependence of DNA melting temperature on pH and salt concentration. In the present work, we report a single-molecule study of the stability of DNA against denaturation when subjected to changes in solvent. We investigated the appearance of DNA instability under specific external applied force and imposed twist values, which was revealed by an increase in the temporal fluctuations in the DNA extension. These fluctuations occur in the presence of a continuous interval of equilibrium states, ranging from a plectonemic state to a state characterized by denaturation bubbles. In particular, we observe the fluctuations only around a characteristic force value. Moreover, this characteristic force is demonstrated to be notably sensitive to variations in the pH and ionic strength. Finally, an extension of a theoretical model of plectoneme formation is used to estimate the average denaturation energy, which is found to be linearly correlated to the melting temperature of the DNA double strands.
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