Electrical energy can be obtained from the controlled mixing of fresh (river) and saline (sea) water. Existing technologies such as pressure retarded osmosis and reverse electrodialysis make use of ion-exchange membranes which must be crossed by either the water or the ions. Recently a new physical principle has been experimentally demonstrated, which allows extraction of electrical energy without making use of membranes, based on the temporary storage of ions inside two porous electrodes kept at different electrical potentials, and the repeatable expansion/contraction of the electrostatic double layers formed inside the electrodes upon changing the salt concentration [D. Brogioli, Phys. Rev. Lett., 2009, 103, 058501]. To make further investigations and to improve the energy recovery, we developed a simple prototype cell of much larger dimensions. Because of the larger dimensions (thus higher currents), testing is more facile, while this design can be the basis for further scaling-up of this technology. In order to reduce the internal resistance of the cell, the electrodes are no longer placed side-by-side, but parallel to one another, separated only by a 250 μm-thick open spacer channel to form a “sandwich”-like flow cell. In a lab-scale experimental stack consisting of 8 such cells (with outer dimensions 6 × 6 × 1 cm³) we extract about 2 J per charging/discharging cycle in 500 mM/1 mM NaCl salt solution, an amount which is 20 times higher per cycle per unit electrode mass than previously obtained. The extracted energy increases with the operating voltage, in line with predictions of the Gouy-Chapman-Stern model for double layer formation.

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.